Note: Descriptions are shown in the official language in which they were submitted.
j ~3c~c~4~i2
LIQUID NONIOI~IC LAU~DR~ DETEI~GENT COI~POSITION
COI~TAINING ALKYL SULFONATE OR ALKYL ETHE~ SULFATE STABIL]ZEI~
AND 1\1ETHOD OF USE
ACKCROUND OF TI~E I~VENTION
(1) Field of Invenlion
This invention relales to nonaqueous llquid rnbric lrenting !
compositions. More pnrliculQrly, this Invention relates to nonaqueous liquid ¦
laundry de~ergent compositlons which are stable agninst phase separa~;on a~
gelalion and are e~sily pourable and to the use ol these compositions lor
cle~ning soiled fabrics.
(2) Discussion of Prior Art
Liquid nonaqueous heavy du~y laundry de~ergent compositions arc well
known in ~he art. For instance, compositions of that type may comprise
liquid nonionic surfnctant in which are dispersed particles of a builder, as
sho~ n for instance in the U.S.P. Nos. 4, 316,812, 3,630,929 and 4 ,264,466
and British Patent Nos. 1,205,711, 1,270,040 and 1,600,981.
Related Canadian patent appliaations assigned to the cc~mDn assignee are
498,815, filed Dec~ber 31, 1985;
478,380, filed April 4, 1985;
478,379, filed Ap~il 4, 1985; and
502,998, filed E~uary 28, 1986.
These applications are directed to liquld nonsqueous nonionic laundry
detergent compositions.
Liquid detergents are often considered to be more convenicnt to employ
than dry powdered or partlculate products and, therefore, havc lound
substantial favor with consumers. They sre readily measurable, speedily
;¦ dissolved in lhe wash water, capable of being easily applied in concentrated ~
solutions or dispersions to soiled arens on garments to be Isundered and are j
¦ non-dusting, and they ususlly occupy less storage space. Additionnlly, the
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liquid eterge~ts m~y have incorporated in their lorm~llations m=terialc which
could not stand drying operations without deterioration, which materials are
often desirably employed in the manufacture of particulate detergent
products. Although they are possessed of many advantages over unitary or
particulate solid products, liquid detergents often have certain inherent
disadvantages too, which have to be overcome to produce acceptable
commercial detergent products. Thus, some such products sepnrate out on
storage and others separate out on cooling and are not readily redispersed.
In some cases the product viscosity changes and it becomes either too thic};
lQ to pour or so thin as to appear watery. Some clear products become cloudy
and others gel on standing.
The present inventors have been involved in studying the behavior of
nonionic liquid surfactant systems with particulate matter suspended therein.
Of particu~ar interest has been nonaqueous built laundry liquid detergent
compositions and the problem of settling of the suspended builder and other
laundry additives as well as the problem of gelling associated with nonionic
surfactants. These considerations have an impact on, for example, product
stability, pourability and dispersibility.
lt is known that one of the major problems with built liquid laundry
detergents is their physical stability. This problem stems from the fact th~t
the density of the solid particles dispersed in the nonionic liquid surfactant
is higher than the density of the liquid surfactant.
Therefore, the dispersed particles tend to settle out. Two basic
solutions exist to solve the settling out problem: increase nonionic liquid
2 5 viscosity and reduce the dispersed solid particle size .
It is known that suspensions can be stabilized against settling by
adding inorganic or organic thickening agents or dispersants, such as, for
example, very high surface area inorganic materials, e. g. finely divided
silica, clays, etc., organic thickeners, such as the cellulose ethers, acrvlic
and acrylamide polymers, polyelectrolytes, etc. However, such increases in
~ ~3~C)46Z - j
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suspensio~ viscosity are naturally limited by the requirement that the liquic~
suspension be readily pourable and flowable, even at low temperature.
Furthermore, these additives do not contribute to the cleaning performancc
l of the formulation.
1 Grinding to reduce the particle size provides the following advantages:
1. Specific surface area of the dispersed particles is increased, and,
therefore, particle wetting by the nonaqueous vehicle (liquid nonionic) i
proportionately improved.
2. The average distance between dispersed particles is reduced with 8
proportionate increase in particle-to-particle interaction. Each of these
effects contributes to increase the rest-gel strength and the suspension yield
stress whi]e at the same time, grinding significantly reduces plastic
viscosity.
The yield stress is defined as the minimum stress necessary to induce 8
plastic deformation (flow) of the suspension. Thus, visualizing the
suspension as a loose network of dispersed particles, if the applied stress is
lower than the yield stress, the suspension behaves like an elastic gel and
no plastic flow will occur. Once the yield stress is overcome, the networl;
breaks at some points and the sample begins to flow, but with a very high
apparent viscosity. If the shear stress is much higher than the yield
stress, the pigments are partially shear-deflocculated and the apparent
viscosity decreases. Finally, if the shear stress is much higher than the
yield stress value, the dispersed particles are completely shear-deflocculated
and the apparent viscosity is very low, as if no particle interaction were
2 5 present .
Therefore, the higher the yield stress of the suspension, the higher
the apparent viscosity at low shear rate and the better is the physical
stability against settling of the product.
In addition to the problem of settling or phase separation the
nonaqueous liquid laundry detergents basèd on liquid nonionic surfactants
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13C~)462 - I
suff~r from the drawback that the nonionics tend to gel when added to cold
u ater This is a particularly important problem in the ordinary use of
European household automatic washing machines where the user places thc
laundry detergent composition in a dispensing unit (e. g. a dispensin~
drawer) of the machine. During the operation of the machine the detergent
in the dispenser is subjected to a stream of cold water to transfer it to th
main body of wash solution. Especially during the winter months when the
detergent composition and water fed to the dispenser are particularly cold,
the detergent viscosity increases markedly and a gel forms. As a result
some of the composition is not flushed completely off the dispenser durin g
operation of- the machine, and a deposit of the composition builds up wit~
repeated wash cycles, eventually requiring the user to flush the dispenser
with hot water.
The gelling phenomenon csn also be a problem whenever it is desired to
carry out washing using cold water as may be recommended for certain
synthetic and delicate fabrics or fabrics which can shrink in warm or hot
water .
The tendency of concentrated detergent compositions to gel during
storage is aggrevated by storing the compositions in unheated storage areas,
or by shipping the compositions during winter months in unheated
transportation vehicles.
Partial solutions to the gelling problem have been proposed, for
example, by diluting the liquid nonionic with certain viscosity controlling
solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol
(see U.S.P. 3,953,380), alkali metal formates and adipates (see U.S.P.
4,368,147), hexylene glycol, polyethylene glycol, etc. and nonionic structure
modification and optimization. As an example of nonionic surfactant
modification one particularly successful result has been achieved by
acidifying the hydroxyl moiety end group of the nonionic molecule. The
advantages of introducing a carboxylic acid at the end of the nonionic
1 1300462 - ~
ll
include gel inhibition upon dilution; decreasing the nonionic pour point; and;
formation of an anionic surfactant when neutrglized in the washing liquor.
Nonionic structure optimization has centered on the chain length of the
hydrophobic-lipophilic moiety gnd the number and make-up of alkylene o~ide
(e. g. ethylene oxide) units of the hydrophilic moiety. For example, it ha~
been found that a C13 fatty alcohol ethoxylated with 8 moles of ethylen~
oxide presents only a limited tendency to gel formstion.
Nevertheless, improvements are desired in both the stability and ge~
inhibition of nonaqueous liquid fabric treating compositions.
BRIEF DESCRIPTION OF THE INVENTION
In accordance with the present invention 8 highly concentrated stab]e
nonaqueous liquid laundry detergent composition is prepared by adding to
the composition small effective amounts of a higher alkyl sulfonate or higher
slky1 polyether sulfate anti-settling stabilizing additive.
The compositions of the present invention contain as an essentisl
ingredient a higher alkyl sulfonate or higher alkyl polyether sulfate
anti-settling stabilizing additive. The anti-settling stabilizing additives are
anionic surfactants. The anionic surfactants that are useful in the present
invention are those surface active compounds which contain a long chain
hydrocarbon hydrophobic group in their molecular structure and a
hydrophile group, i . e . water solubilizing group such as sulfonate or sulfate
group. The anionic surfactants include the water soluble higher alkyl
sulfonates and the water soluble higher alkyl polyether sulfates.
The preferred anionic surface active agents are alkane, i . e . alkyl
primary and secondary sulfonates, in which the alkyl group contains 8 to 26
carbon atoms, preferably 12 to 22 carbon atoms and more preferably 14 to 18
carbon atoms.
The alkyl sulfonates can be used as the alkali metal salts, such as
sodium and potassium, the alkaline earth metal salts, such as calcium,
- 130~46Z 6230l-l43g
magnesium and barium, and the ammonium cation salt. The pre-
ferred salts are the sodium and potassium salts.
The alkyl ether sulfates used as an anti-settling
stabilizing additive in accordance with the present invention
can be normal or branched chain alkyl and contain lower alkoxy
groups, which can contain two or three carbon atoms.
The preferred alkyl poly lower alkoxy sulfates used
in accordance with the present invention are the alkyl poly
ethoxy sulfates represented by the formula
R-O-(CH2CH20)p-S03M,
wherein R is a Cg_C20 alkyl, preferably C14 to C20 or Clo to
Clg and more preferably C12 to Cls: p is 2 to 8, preferably 2
to 6, and more preferably 2 to 4; and M is an alkali metal,
such as sodium and potassium, an alkaline earth metal, such as
calcium, magnesium and barium and ammonium cation. The sodium
and potassium salts are preferred.
In order to improve the viscosity characteristics of
the composition an acid terminated nonionic surfactant can be
added. To further improve the viscosity characteristics of the
composition and the storage properties of the composition there
can be added to the composition viscosity improving and anti
gel agents such alkylene glycol mono alkyl ethers and addition-
al anti-settling agents such as phosphoric acid ester and alu-
minum stearate. In preferred embodiment of the invention the
detergent composition contains an acid terminated nonionic
surfactant, an alkylene glycol mono alkyl ether and an alkyl
sulfonate or alkyl ether sulfate stabilizing anti-settling
agent.
Sanitizing or bleaching agents and activators there-
- 7 -
1300462 62301-1439
for can be added to improve the bleaching and cleansing charac-
teristics of the composition.
In an embodiment of the invention the builder compon-
ents of the composition are ground to a particle size of less
than 100 microns and to preferably less than 10 microns to
further improve the stability of the suspension of the builder
components in the liquid nonionic surfactant detergent.
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130~46Z
In addition other ingredients csn be added to the composition such ac
anti-incrustation agents, anti-foam agents, optical brighteners, enzyme~,
anti-redeposition agents, perfume and dyes.
The presently manufactured washing machines for home use normal]~
operate at washing temperatures of up to 100~C. About up to 18 gallons (70
liters) of water sre used during the wash and rinse cycles.
About 250 gms of powder detergent per wash is normally used.
In accordance with the present invention where the highly concentrated
liquid detergent is used norm~ly only 100 gms (77 cc) of the liquid
detergent composition is required to wash a full load of dirty laundry.
Accordingly, in one aspect the present invention provides a liquid
heavy duty laundry composition composed of a suspension of a detergent
builder salt in a liquid nonionic surfactant wherein the composition includes
an amount of a higher alkyl sulfonate or a higher alkyl polyether sulfate to
increase the stability of the suspension against settling.
According to another sspect, the invention provides a concentrated
liquid heavy duty laundry detergent composition which is stable, non-settling
in storage and non-gelling in storage and in use. The liquid compositions of
the present invention are easily pourable, easily measured and easily put
20 ¦ into the washing machine.
According to another aspect, the invention provides a method for
dispensing a liquid nonionic laundry detergent composition into and/or with
cold water without undergoing gelation. In particular, a method is provided
for filling a container with a nonaqueous liquid laundry detergent composition
2 5 in which the detergent is composed, at least predominantly, of a liquidnonionic surface active agent and for dispensing the composition from the
container into an aqueous wash bath, wherein the dispensing is effected by
directing a stream of unheated water onto the composition such that the
composition is carried by the stream of water into the wash bath.
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1 3~ 0 4 6 Z 62301-1439
ADVANTAGES OVER THE PRIOR ART
The addition of the higher alkyl sulfonates and higher
alkyl polyether sulfates to the detergent compositions reduce the
problem of dispersed particle settling and phase separation.
The concentrated nonaqueous liquid nonionic surfactant
laundry detergent compositions of the present invention have the
advantages of being stable, non-settling in storage, and non-
gelling in storage. The liquid compositions are easily pourable,
easily measured and easily put into the laundry washing machines.
The present invention seeks to provide a stable liquid
heavy duty nonaqueous nonionic detergent composition containing
at least one anti-settling stablizing agent and at least one
builder salt suspended in a nonionic surfactant.
The invention also seeks to provide liquid fabric
treating compositions which are suspensions of insoluble in-
organic particles in a nonaqueous liquid and which are storage
stable, easily pourable and dispersible in cold, warm or hot
water.
This invention seeks to formulate highly built heavy
duty nonaqueous liquid nonionic surfactant laundry detergent
compos1tions which can be poured at all temperatures and which
can be repeatedly dispersed from the dispensing unit of European
style automatic laundry washing machines without fouling or
plugging of the dispenser even during the winter months.
This invention seeks to provide non-gelling, stable
suspensions of heavy duty built nonaqueous liquid nonionic
laundry detergent composition which include an effective amount
of a higher alkyl sulfonate or a higher alkyl polyether sulfate
which is sufficient to increase the yield stress of the compo-
sition to thereby increase it stability, i.e. prevent settling of
buiIder particles, etc., preferably while reducing or at least
~30 without increasing, the plastic viscosity (viscosity under shear
B g
~ `` 130046Z 62301-1439
conditions) of the composition.
The invention will become more apparent from the
following detailed description of preferred embodiments
generally provided for by preparing a detergent composition by
adding to the nonaqueous liquid nonionic surfactant an effective
amount of a higher alkyl sulfonate or a higher alkyl palyether
sulfate anti-settling agent sufficient to inhibit settling of the
suspended particles, wherein said composition includes inorganic
or organic fabric treating additives, e.g. viscosity improving
and one or more anti-gel agents, anti-incrustation agents,
pH control agents, bleaching agents, bleach activators, anti-
foam agents, optical brighteners, enzymes, anti-redepostion
agents, perfume and dyes.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention the physical
stablity of the suspension of the detergent builder compound or
compounds and any other suspended additive, such as bleaching
agent, etc. in the liquid nonionic surfactant vehicle is substan-
tially improved by the addition of an anti-settling stabilizing
agent which is an anionic surfactant higher alkyl sulfonate or an
anionic ~urfactant higher alkyl polyether sulfate.
The addition of very small amounts of the anionic sur-
factant anti-settling stabilizing agents is sufficient to sub-
stantially improve the physical stability of the detergent
compositions.
The anionic higher alkyl sulfonate and higher alkyl
polyether sulfate surfactants are commercially available and/or
can readily be manufactured by known procedures.
The compo~itions of the present invention contain as
an essential ingredient a higher alkyl sulfonate or a higher
alkyl polyether anti-settling stablizing additive. The anti-
--10-
D
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13~)0462
62301-1439
~ettling stabilizing additive can comprise one or more anionic
surface active agents.
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130046Z
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The anionic surface active agents that are useful in
the present invention are those surface active compounds which
contain a long chain hydrocarbon hydrophobic group in their
molecular structure and a hydrophile group, i.e. water solubil-
izing group such as sulfonate or sulfate group.
The anionic surface active agents include the water
soluble higher alkyl sulfonates and the water soluble higher
alkyl poly ether sulfates.
The preferred anionic surface active agents are
alkane, i.e. higher alkyl primary and secondary sulfonates, in
which the alkyl group contains 8 to 26 carbon atoms, preferably
12 to 22 carbon atoms and more preferably 14 to 18 carbon
atoms.
The primary and secondary alkyl sulfonates can be
made by reacting long chain alpha-olefins with sulfites or
bisulfites, e.g. sodium bisulfite.
The alkyl sulfonates can also be made by reacting
long chain normal paraffin hydrocarbons with sulfur dioxide and
oxygen as described in U.S.P. Nos. 2,503,280, 2,507,088,
3,372,188 and 3,260,741 to obtain normal or secondary higher
alkyl sulfonates suitable for use as surfactant detergents.
The alkyl substituent is preferably linear, i.e.
normal alkyl, however, branched chain alkyl sulfonates can be
employed, although they are not as good with respect to biode-
~ gradability. The alkane, i.e. alkyl, substituent may be ter-
-~ minally sulfonated or may be joined to the 2-carbon atom of the
chain, i.e. may be a secondary sulfonate.
The higher alkyl sulfonates can be used as the alkali
metal salts, such as sodium and potassium, an alkaline earth,
. ~
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1300462 62301-1439
metal salts, such as calcium, magnesium and barium, and the
ammonium cation salt. The preferred salts are the sodium and
potassium salts.
The more preferred alkyl sulfonates are the C14 to
Clg preferably C14 to C16 primary normal alkyl sodium and
potassium sulfonates, with the Cls primary normal alkyl sodium
sulfonate salt being the most preferred. The Cls normal pri-
mary
`~
,
~:
lla
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. ~
~` 130046Z 62301-1439
alkyl sodium sul fonate salt is sold under the tradename Mersolat
H 98 (C15).
The higher alkyl sulfonates are generally more effect-
ive than the higher alkyl polyether sulfates.
Mixtures of higher alkyl sulfonates can be used as
well as mixtures of higher alkyl sulfonates and higher alkyl
polyether sulfates.
The higher alkyl polyether sulfates used as an anti-
settling stablizing additive in accordance with the present in-
vention can be normal or branched chain alkyl and contain lower
alkoxy groups which can contain two or three carbon atoms. The
normal higher alkyl polyether sulfates are preferred in that
they have a higher degree of biodegradability than the branched
chain alkyl and the lower poly alkoxy groups are preferably
ethoxy groups.
The preferred higher alkyl poly ethoxy sulfates used
in accordance with the present invention are represented by the
formula
Rl-o(CH2CH20)~-S0 3M ~
wherein Rl is a C to C alkyl, preferably C to C and more
8 20 10 18
preferably C12 to C14 or C15;p is 2 to 8, preferably 2 to 6, and
more preferably 2 to 4; and M is an alkali metal, such as sodium
and potassium, and alkaline earth metal, such as calcium, mag-
nesium and barium, and ammonium cation. The sodium and potas-
sium salts are preferred.
A preferred higher alkyl poly ethoxylated sulfate is
the sodium salt of a triethoxy C12 to C15 alcohol sulfate having
the formula
12-15 0-(cH2cH2o)3-so3Na
Examples of other suitable higher alkyl poly lower
~30 alkoxy sulfates that can be used in accordance with the present
12-
.--~. . ,
, ~ . , .
13~0462 62301-1439
invention are C12 15 normal or primary alkyl triethenoxy
sulfate, sodium salt: n-decyl diethenoxy sulfate, sodium salt;
C12 primary alkyl diethenoxy sulfate, ammonium salt: C15
primary alkyl tetraethenoxy sulfate, sodium salt: mixed C14 15
normal primary alkyl mixed tri- and tetraethenoxy sulfate,
sodium salt: stearyl
12a-
~ ~300462
pentaethenoxy sulfate, sodium. salt; and mixed C10_18 normal primary alky~
triethenoxy sulfRte, potassium salt.
The normal alkyl poly-lower alkoxy s~lfates are readily biodegradable
and are preferred. The alkyl poly-lower alkoxy sulfates can be used in
mixtures with each other and/or in mixtures with the above discussed higher
alkyl sulfonates.
Although applicants do not wish to be bound by any particular theory
of the manner by which the anionic surfactants function to prevent settlin g
of the suspended particles, it is presumed that the alkyl sulfonates or alkyl
ether sulfates increases the wettability of the dispersed solid particle
surfaces by-the nonionic surfactant. This increase in wettability, therefore,
allows the suspended particles to more easily remain in suspension.
The increased physical stability is manifested by an increase in the
J l ~ yield stress of the composition by as much as about 100% or more, for
~ example, in the case of Mersolat H98(C15) from 2 Pa to g Pa, as compared to
the same composition without the stabilizing sgent. As described above, the
higher is the yield stress, the higher is the apparent viscosity at low shear
rate and the better is the physical stability.
Only very small amounts of the higher alkyl sulfonates or higher alkyl
polyether sulfates stabilizing agent is required to obtain the significanl
improvements in physical stability. For example, based on the total weight
of the nonionic liquid surfactant composition, suitable amounts of the higher
alkyl sulfonate or higher alkyl polyether sulfate are in the range of from
about 0 .1% to about 5%, preferably from about 0 . 3% to about 2 . 0% and more
preferably about 0 . S to 1. 5% .
In addition to its action as a physical stabilizing agent, the higher alkyl
sulfonates and higher alkyl polyether sulfates have the additional advantages
over other physical stabilizing agents that they are nnionic in character and
are compatible with the nonionic surfactant component and exhibit some
detergent activity.
13
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While the higher alkyl sulfonates or higher alkyl polyether sulf~tes
alone are effective in their physicnl stabilizing action, there can be ~dde~ to
the formulation other known physical stabilizers, such as, for exsmple, an
acidic organic phosphorus compound having an acidic - POH group, such as
a partial ester of phosphorous acid and an alkanol or an aluminum salt of a
fatty acid.
Nonionic Surfactant Detergent
The nonionic synthetic organic detergents employed in the practice of
the invention may be any of a wide variety of known compounds.
As is well 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 sttached to
the nitrogen can be condensed with ethylene oxide 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 U.S.
patents 4,316,8~2 and 3,630,929.
Vsually, the nonionic detergents are poly-lower alkoxylated lipophiles
wherein the desired hydrophile-lipophile balance is obtained from addition of
a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred
class of the nonionic detergent employed is the poly-lower alkoxylated higher
alkanol wherein the alkanol is of 9 to 18 carbon atoms and wherein the
number of mols of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to
12. Of such materials it is preferred to employ those wherein the higher
alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and
~30 which contain from 5 to 8 or 5 to 9 lower alkoxy groups per mol.
14
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1300462 ~
Preferably, the lower alkoxy is ethoxy but in some instances, it m~y be
desirably mixed with propoxy, the latter, if present, often being a minor
(less than 50~) proportion.
Exemplary of such compounds are those wherein the alkanol is of 12 to
15 carbon atoms and which contain about 7 ethylene oxide groups per mol,
e.g. Neodol 25-7 and Neodol 23-6.5, which products are made by Shel]
Chemical Company, Inc. The former is a condensation product of a mixture
of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7
mols of ethylene oxide and the latter is a corresponding mixture wherein the
carbon atom content of the higher fatty alcohol is 12 to 13 and the number
of ethylene oxide groups present averages about 6 . 5 . The higher alcohols
are primary alkanols. ~
Other examples of such detergents include Tergitol 15-S-7 and Tergitol
15-S-9, both of which are linear secondary alcohol ethoxylates made by
Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15
¦ carbon atoms linear secondary alkanol with seven mols of ethylene oxide and
¦ the latter i8 a similar product but with nine mols of ethylene oxide being
¦ reacted.
¦ Also useful in the present composition as a component of the nonionic
I detergent are higher molecular weight nonionics, suah as Neodol 45-11,
which are similar ethylene oxide condensation products of higher fatty
alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and
the number of ethylene oxide groups per mol being about 11. Such products
are also made by Shell Chemical Company.
Othér useful nonionics are represented by the commercially well known
class of nonionics sold under the trademark Plurafac. The Plurafacs are the
reaction product of a higher linear alcohol and a mixture of ethylene and
propylene oxides, containing a mixed chain of ethylene oxide and propylene
~; ~ oxide, terminated by a hydroxyl group. Examples include Product A (a
C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles
. . . , ~
~ i30046;Z
propylene oxide), Product B (a C13-C15 fatty alcohol condensed with 7 moles
propylene oxide and 4 moles ethylene oxide), Product C (a C13-C15 fatt~
alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide,
Plurafac B26), and Product D (a mixture of equal parts Product C and
Product B ) .
Another group of liquid nonionics are commercially available from Shell
Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 is an
ethoxylated Cg-Cll fatty alcohol with an average of 5 moles ethylene oxide
and Dobanol 25-7 is an ethoxylated Cl2-Cl5 fatty alcohol with an s~erage of
7 moles ethylene oxide per mole of fatty alcohol.
In the preferred poly-lower alkoxylated higher alkanols, to obtain th~
best balance of hydrophilic snd lipophilic moieties the number of lower
alkoxies will usually be from 40% to 100% of the number of carbon atoms in
the higher alcohol, preferably 40 to 60% thereof and the nonionic detergent
will preferably contain at least 50% of such preferred poly-lower alkoxy
higher alkanol. Higher molecular weight alkanols and various other normally
solid nonionic detergents and surface active agents may be contributory to
gelation of the liquid detergent and consequently, will preferably be omitted
or limited in quantity in the present compositions, although minor
proportions thereof may be employed for their cleaning properties, etc. With
respect to both preferred and less preferred nonionic detergents the alkyl
groups present therein are generally linear although branching may be
tolerated, such as at a carbon next to or two carbons removed from the
terminal carbon of the straight chain and away from the ethoxy chain, if
2 5 such branched alkyl is not more than three carbons in length . Normally,
the proportion of carbon atoms in such a branched configuration will be
~; minor rarely exceeding 20% of the total carbon atom content of the alkyl.
Similflrly, although linear alkyls which are terminally joined to the ethylene
oxide chains are highly preferred and are considered to result in the best
combination of detergency, biodegradability and non-gelling characteristics,
16
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1 13~)0~6Z-
medial or secondary joinder to the ethylene oxide in the chain may occur. It
is usually in only a minor proportion of such alkyls, generally less than 20
but, as is in the cases of the mentioned Terigtols, may be greater. Also,
when propylene oxide is present in the lower alkylene oxide chain, it wil~
usually be less than 20% thereof and preferably le6s than 10% thereof.
When greater proportions of non-terminally alkoxylated alkanols,
propylene oxide-containing poly-lower alkoxylated alkanols and less
hydrophile-lipophile balanced nonionic detergent than mentioned above ar~
employed and when other nonionic detergents are used instead of the
preferred nonionics recited herein, the product resulting may not have a6
good detergency, stability, viscosity and non-gelling properties 8S the
preferred compositions but use of the vi~cosity and gel controlling
compounds of the invention can also improve the properties of the detergents
based on such nonionics. In some cases, as when a higher molecular weight
polylower alkoxylated higher alkanol is employed, often for it6 detergency,
the proportion thereof will be regulated or limited in sccordance with the
results of routine experiments, to obtain the desired detergency and 6till
have the product non-gelling and of desired viscosity. Also, it has been
found that it is only rarely necessary to utilize the higher molecular weight
nonionics for their detergent properties since the preferred nonionics
described herein are excellent detergents and additionally, permit th~
attainment of the desired viscosity in the liquid detergent without gelation at
low temperatures.
Another useful group of nonionic surfactants are the "Surfactant Tr
series of nonionics availabe from British Petroleum. The Surfactant T
nonionics are obtained by the ethoxylation of secondary C 13 fatty alcohols
having a narrow ethylene oxide distribution. The Surfactant T5 has an
average of 5 moles of ethylene oxide; Surfactant T7 an average of 7 moles of
ethylene oxide; Surfactant T9 an average of 9 moles of ethylene oxide and
17
~ 13~(~46Z
Surfaclant T12 an average ol 12 moles of e~hylene oxide per mole or
s~condnry C13 fatly alcohol.
In the compositions of this invention, preferred nonion;c surrnctants
include the C12-C15 secondary fatty a~cohols with relatively narrow conlents
of ethylene oxide in the range of from about 7 to 9 mole6, snd the C9 to C11
fatty a~cohols ethoxylated with about 5-6 moles ethylene oxide.
I~lixtures of two or more of the liquid nonionic 6urfactant6 cnn be u6ed
and in wme cases advsntage6 can be obtained by the use of 6uch mixture6.
Acid Terminsted Nonionic Surfactant
The viscosity snd gel propertie6 of the liquid detergent composition6
csn be improved by including In the composltion sn effective amount an acid
terminsted liquid nonionic 6urfactsnt. The ~cid termin~ted nonionic
6urfactnnts consi6t of 8 nonionic surfactsnt which h~s been modified to
convert ~ free hydroxyl group thereof to B moiety hnving a free carbox~ l
lS group, 6uch as sn ester or ~ psrtisl e6ter of B nonionic 6urfactsnt snd 8
polyc~rboxylic scid or snhydride.
As discl ~sed in the aam~nly assigned CDadi~n patent application Serial
ND. 478,379 filed on P~ril 4, 1985, the free car~aKyl grc~ difie~t nlionic
surfactants, which nEIy
be broAdly characterized ~s polyether csrboxylic acid6, function to lower the
lemper~ture ~t which the liquid nonionic form6 a gel with wster.
The sddition of the acid terminsted nonionic surfect~nts to the liquid
nonionic surfact~nt aids in the di6pen6ib~Uty of the composilion, 1. e .
pour~biUly, sr d lowers the temperature st which the liquid nonionlc
6urf~ct~nts form B gel in w~ter wlthout ~ decre~6e in their st~lbility sg~ln6l
6ellling. The scid terminsled nonionic surf~ctant rescts in the wsshing
mnchine water with the alkalinity of the disper6ed builder 6~1t phsse of the
detergent composition snd scts a8 an eflectlve snlonic 6urfactant.
Specific exemples include the hell-esters of Plurafsc RA30 with 6uccinic
anh~dride, the ester or hslf e6ter ol Dobsnol 25-7 with 6uccinic anhydride,
~ r ~ L
~, ~
.~
13~046Z
and the ester or ha~f ester of Dobanol 91-5 with succinic anhydride. Instea~
of succinic anhydride, other polycarboxylic acids or anhydrides can be used,
e. g. maleic acid, maleic acid anhydride, glutaric acid, malonic acid, ph~halic
acid, phthalic anhydride, citric acid and the like.
The acid terminated nonionic surfactants can be prepared as follows:
Acid Terminated Product A. 400 g of Product A nonionic surfactant
which is a C13 to C15 alkanol which has been alkoxylated to introduce 6
ethylene oxide and 3 propylene oxide unitg per alkanol unit is mixed witn
32g of succinic anhydride and heated for 7 hours at 100C. The mixture is
cooled and filtered to remove unreacted succinic material. Infrared analysis
indicated that about one half of the nonionic surfactant has been converted
to the acidic half-ester thereof.
Acid Terminated Dobanol 25-7. 522 g of Dobanol 25-7 nonionic
surfactant which is the product of ethoxylation of a C12 to Cl5 alkanol and
has about 7 ethylene oxide units per molecule of alkanol is mixed with 100g
of succinic anhydride and 0. lg of pyridine (which acts as an esterification
catalyst) and heated at 260C for 2 hours, cooled and filtered to remove
unreacted succinic material. Infrared analysis indicates that substantially all
the free hydroxyls of the surfactant have reacted.
Acid ~erminate Dobanol 91-5. 1000 g of Dobanol 91-5 nonionic
surfactant which is the product of ethoxylation of a Cg to C11, alkanol an~
has about 5 ethylene oxide units per molecule of alkanol is mixed with 265g
of succinic anhydride and 0. lg of pyridine catalyst and heated at 260C for
2 hours, cooled and filtered to remove unreacted succinic materisl. Infrared
analysis indicates that substantially all the free hydroxyls of the surfactant
; have reacted.
Other este~qfication catalysts, such as an alkali metal alkoxide (e . g.
sodium methoxide) may be used in place of, or in admixture with, thQ
pyridine.
~ : 11 19
: : :
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The acidic polyether compound, i.e. the acid terminated nonionic
surfactant is preferably added dissolved in the nonionic surfactant.
B UILDER SALTS
The liquid nonaqueous nonionic surfactant used in the compositions of
S the present invention has dispersed and suspended therein fine particles of
inorganic andlor inorganic detergent builder salts.
The invention detergent compositions include water soluble and/or water
insoluble detergent builder salts. Water soluble inorganic alkaline builder
salts which can be used alone with the detergent compound or in sdmixture
with other builders are alkali metal carbonates, bicarbonates, borates,
phosphates, polyphosphates, and silicates. (Ammonium or substituted
ammonium salts can also be used. ) Specific examples of such salts are
sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium
pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium
tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium
mono and diorthophosphate, and potassium bicarbonate. Sodium
tripolyphosphate (TPP) is especially preferred.
Since the compositions of this invention are generally highly
l concentrated, and, therefore, may be used at relatively low dosages, it i~
1 desirable to supplement any phosphate builder (such as sodium
l tripolyphosphate) with an auxiliary builder such as a poly lower carboxylic
¦ acid or a polymeric carboxylic acid having high calcium binding capacity to
¦ inhibit incrustation which could otherwise be caused by formation of an
l insoluble calcium phosphate.
¦ A suitable lower poly carboxylic acid comprises slkali metal salts of
¦ lower polycarboxylic acids, preferably the sodium and potassium salts.
¦ Suitable lower polycarboxylic acids have two to four carboxylic acid groups.
¦ The preferred sodium and potassium lower polycarboxylic acids salts are the
¦ citric and tartaric acid salts.
I
~ ~ ~ I
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I 13~046Z
l The sodium citric ncid sslts sre the most preferred especisll~ the
¦ lrisodium citrnte. The monosodium gnd disodium citrstes csn slso be useLI.
The monosodium and disodium t~r~Aric ~cid s~ts can ~so be used. The
1 slksli metsJ lower polycgrboxylic 8cid 60.1t8 ~re par~icul~rly good buildcr
¦ salts; bec~use of their high ca~cium and magnesium binding csp~city the
inhibit Incrustation which could otherwise be c8used by lormQtion of insoluble
cslciumsndmsgnesiumssltS-
Other orgllnic builders sre polymers gnd copolymers of polyacrylic ~ci~
1 snd polym~elc snhydride ~nd the 81kali met81 6g~t6 thereof. More specificsll~-
l such builder 6sl~s csn consist of a copolymer which i6 the resction product
of nbout equsl moles of methscryUc gcid and msleic anhydride wh~ch hss been
completely neutrnlized to form the sodium aalt thereof. The builder is
commerci~lly avsilsble under the trad~rk of Sokslsn CP5. This builder
1 6erves when used even in smsll smounts to inhibit incruststion.
Exsmples of orgsnic slksline 6equestrsnt builder 6slts which c~n be
used with the detergent builder sslts or in sdmixture with other orgsnic snd
inorgsnic builders sre slksli metsl smmonium or substituted smmonium
aminopolycsrboxylste6 e. g. 60dlum snd potsssium ethylene
disminetelrsscetste (EDTA) sodium and potassium nitrilotriacetste6 (NTA)
and triethanolsmmonium N-(2-hydroxyethyl)nitrilodiscetstes. Mixed 6slt6 of
these sminopolycarboxylstes sre 81so 6uitsble.
Other su~tsble bullders of the organic type include
carboxymethylsuccinstes tsrtronste6 snd glycollates. Of specisl vslue sre
the polyscetsl csrboxylstes. The polyscetsl csrbo~cylstes ~nd their use in
detergent compositions sre descrlbed in Car~dian pa~ent aE~licati~n ND. 516,256,fil~d August 19 . 1986 assigned to aE~licants assignee and in a U.S.P. Ibs.
4,144,226, 4,315,092 and 4,146,495.
The slksli metol silicstes are useful builder sslts which slso function to
sdjust or control the pH snd to mske the composition snticorrosive to
¦ wsshing machine psrts. Sodium silicates of Ns20/SiO2 rstios of from 1.6/1
21
: ' I
I
1 13V0462
¦ to 1/3.2, especlally ~bout 112 to 1/2.B are preferred. Potnssium silic~tes of
lhe snme rnlios cnn nlso be used.
Olher typical suitnble builders include, for example, those disclosed in
U.S. Palents 4,316,812, 4,264466 and 3,630,929. The inorg~n~c builder
sa1ls cnn be used with the nonionic surfgctan~ detergent compound or in
sdmixture wilh other inorg~nic builder 6alts or with orgnnlc builder 6alt6.
The wsler insoluble crystalline and amorphoug alumlnosilicate zeolile~
can be used. The zeolite6 generally huve the formula
(M20)X- (A1203)y (Si2)z WH2
wherein x is 1, y i6 from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5
or higher nnd prelerably 2 to 3 and w i6 from 0 to 9, prefer~bly 2.5 lo G
and M is preferably sodium. A typical zeolite i6 type A or 6imilnr 6tructure,
with type 4A particularly preferred. The preferred aluminosilicates hnve
calcium ion exchange capacities ot about 200 milliequivalent6 per gram or
greater, e. g. 400meq Ig.
Various crystallJne zeolites ~i.e. alumino-silicste6) that can be u6ed are
described in Britlsh Pa~ent 1,504,168, U.S.P. 4,409,136 and Can~dian
P~tents 1,07 ~,835 and 1,087,477,
An example of amorphous zeolites u6eful
herein can be tound in Pelgium Patent 835,351,
Other m~tcriois 6uch as clsys, particularly Or the water-insoluble types,
¦ may be useful adj~ncts in compositions of this invention. Particularly useful
¦ i6 bentonite. This material i6 primarily montmorillonite which i6 a hydrated
25 ¦ aluminum silicate in which about 1/6th Or the aluminum atom6 msy be replaced
by magnesium ~toms ~nd with which varying amounts of hydrogen, sodium,
potassium , calcium , etc ., may be loosely combined . The bentonite in its
more puri~ied form ~i . e . lree from any grit, 6and, etc . ) suitable ~or
detergents contains at leasl 509~ montmorillonite and thus it8 cation exch~nge
22
: : ~
~ ` ~
I 13C1 046Z
capacity is ~t least about 50 to 75 meq per lOOg of bentonite. Particularly
preferred bentonites are the Wyoming or Western U.S. bentonites which have
been sold as Thixo-~e~s 1, 2, 3 and 4 by Georgia Kaolin Co. These
bentonites are known to soften textiles as described in British P~tent 401,413
to Marriott and British Patent 461,221 to Marriott and Guan.
Viscosity Control ~nd Anti Gel Agents
The inclusion in the detergent composition of an effective amount of lo~
molecular weight amphiphilic compounds which function as viscosity control
and gel-inhibiting agents for the nonionic 6urfactant substantially improves
the storage properties of the composition. The amphiphilic compounds can
be considered to be analagous in chemical gtructure to the ethoxylated
and/or propoxylated fatty alcohol liquid nonionic surfactants but have
relatively short hydrocarbon chain lengths (C2 to C8) and a low content of
ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).
Suitable amphiphilic compounds can be represented by the following
general formula
RO(CH2CHaO)nH
where R is a C2-C8 alkyl group, and n is a number of from about 1 to
6, on average.
Specifically the compounds are lower (C2 to C3) alkylene glycol mono
lower (C2 to C5) alkyl ethers.
I~ore specifically the compounds are mono di- or tri lower (C2 to C3)
alkylene glycol mono lower (Cl to C5) alkyl ethers.
Specific examples of suitable amphiphilic compounds include
ethylene glycol monoethyl ether (C2H5-O-CH2CH2OH),
diethylene glycol monobutyl ether (C4Hg-O-(CH2CH2O)2H),
tetraethylene glycol monobutyl ether ~C4H7-O-(CH2CH2O)4H) and
dipropylene glycol monomethyl ether (CH3-O-(CH2CHO)2H Diethylene glycol
CH3
monobutyl ether is especially preferred.
23
:
1;~ 46Z
The incluslon in the composition ol the low molecular weight lower
all;y1ene gl~, col mono alkyl ether decrenses the viscosity of the composition,
such thn~ i- is more easily pourable, improves the ~tabillty agsinst 6ettlin6
and improves the dlsperslbllity of the composition on the ~ddition to warm
~ ~ter or cold water.
The compositions of the present invention have improved viscosity and
stability characteristics and remain gtable end pourable at temperatures ~s
low as sbout 5C and lower.
In an embodiment of this invention a supplemental etsbilizing agent
which is an n~kanol ester of phosporic acid or an aluminum salt of B highcr
fatty acid can be added to the formulation.
Improvements in 6tability of the composition may be achieved b)
incorporation of 8 6mall elfective amount of en acidic organic phosphorus
compound having an acidic - POH group, such a6 a partial ester of
phosphorous acid and an alkanol.
As aisclosed in the aalmnly assigned ~ir~ Canadian patent aFplicatio
Seri~l ND. 478,379 filed AEril 4, 1985, the acidic organic ~ ~pwnd
having an acidic - EW
group can lncresse the stabllity of the 6uspen610n of builder6 ~n the
nonaqueous liquid nonlonic 6urlactant.
The scidic organic phosphorus compound msy be, lor instnnce, a psrtial
ester of phosphoric scid and an alcohol 6uch as an alkanol whlch hss a
lipophilic charscter, having, for in8tance, more than 5 carbon atoms, e.g. 8
to 20 carbon stoms.
2 5 A specific example 18 a partial ester of phosphoric acid and a C 16 to
C18 alkanol (Empiphos 5632 from Marchon); it i8 made up of about 35
monoester ond 659~ diester.
The inclusion ol quite smsll amounts of the acidic organic phosphorus
; compound ~nskes the suspension stablè against settling on standing but
::
~ 24
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,~ ~
13~46Z
remains pourable, while, for the low concenlration of st~bilizer, e.g. bclo~
nbout 1~, its plastic viscosity will generolly decrease.
Improvements in the stsbility and snti-6ettling properties of the
composition may s~so be achieved by the addl~on of a 6mal1 efrective ~moun~
S of nn aluminum salt of a higher fatty acld to the composJtlon.
lhe aluminun salt st~bilizing agents are t-he subject matter of the
wmmly assigned ~nadian patent application Serial ND. 502,998, filed
Fe~U~LLry 28, 1986.
The preferred higher sîlphat~c fstty ~c~ds w111 hllve from aboul 8 to
about 22 carbon ntom6, more preferably from ~Ibout 10 to 20 carbon ~tom6,
and especially preferably from about 12 to 18 cnrbon atoms. The aliphatic
rodical mny be saturated or unsaturated and may be atraight or branched.
As in the case ol the nonionic 6urfactants, mixtures of fatty acids may al60
be used, such ss those derived from nstural 60urce6, 6uch as tallow fatty
acid, coco fatty acid, etc.
Examples Or the fatty scids from which the aluminum ~alt stabilizer6 can
be formed include, decanoic scid, dodecsnoic scid, palmitic scid, myri6t~c
scld, stear~c acld, oleic scld, elcosanoic scid, tallow f0tty acid, coco f0tt~
scid, mixlure6 of these acids, etc. The aluminum 6alts ot these acids 0r(
generally commercially svailsble, and are preferably uaed in the triacid form,
e. g. aluminum 6tearate a6 aluminum tristesrate Al(Cl7H35C00)3 . The
monoacld sslts, e.g. aluminum monostearate, Al(OH)2(C17H35C00) and
d~acid salts, e.g. aluminum distearate, Al(OH)(C17H35C00)2, and mix(ures
2~ of two or three of the mono-, di- and triacid aluminum 6alts can 0~80 be
used. It is most preferred, however, that the triacid aluminum 6alt
comprises at least 30%, preferably st lea6t S0%, especially prefersbly at le0st
~; 80% of the total amount ot aluminum fatty acid oalt.
The aluminum salts, as mentioned above, sre commercially svailable and
cnn be easily produced by, for exsmple, ssponifying a fatty acid, e . g.
.
~ 25
~:~
:~
.... . .. .. . . . . ~
130()46Z
~nimol lat, stearic ~cid, elc., followed by tre~tmenl of the resulting so~p
¦ with n~um, aluminn, elc.
Only very small nmounts Or the aluminum salt stnbilizing Agen~ is
required to obtain sn improvement In physical 6t~billty.
1 Bleaching Agent6
The ~bleaching agen~6 are cla66ified broadly, for convenience, a6
chlorine bleaches and oxygen bleacheg. Chlorine bleache6 are typified by
sodium hypochlorite (NnOCI), potassium dichloroisocyanurate (59~ availnble
chlorine), and trichloroisocyanuric ~Icid (959. available chlorine). Oxygen
blcnches are preferred and are repre6cnted by percompound6 whlch libcr~t
hydrogen peroxide in solution. Preferred exampleg include 60dium ond
potassium perborates, percarbonate6, and perpho6ph~lte~, and potassiulr.
monoper6ulfate. The perborates, particularly 60dium perborate monohydrate,
are especiaJly preferred.
The peroxygen compound is preferably u6ed in admixture w~th an
activlltor therefor. Suitable activators which can lower the effective
oper~ting tempernture of the peroxide b1esching agent are di6closed, for
example, in U.S.P. 4,264,466 or in column 1 of U.S.P. 4,430,244,
Polyacyl0ted compounds are preferred activator6; among the6e, compoundE
such as tetraacetyl ethylene diamine (nTAED") and pentaacetyl glucose are
particularly preferred.
Other useful activators include, for exsmple, acetylsalicylic acid
deri~ratives, ethylidene benzoate acetate and lts 6alt6, ethylidene cllrboxyl~teacetate and its 6alts, alkyl and alkenyl 6uccinic anhydride,
tetraacetylglycouril ("TAGV"), and the derivatives ol these. Other useful
~; Qlasses o activator6 are disclosed, for example, in U.S.P. 4,111,826,
4,422,950 and 3,661,789,
The bleach activator usually interacts with the peroxygen compound to
3 0 ~ ~ form a peroxyacid bleaching agent in the wa6h water. It i8 preferred to
26
:
13V~46Z
..
include 8 sequesterin6 agent of high complexing power to inhlbit ~ny
undesired reaction between such peroxyscid nnd hydragen peroxide in the
w~sh solution in the presence of metal ions.
Suit~ble sequestering agents ror this purpose include the sodium 6~1t6
of nitrilotriacetic acid (NTA), e~hylene diamine tetra~cetic acid (EDTA),
diclhylene tr~amine pentaacetlc ac~d (DETPA), dlethylcnc trlnmln~
penlamethylene phosphonic ac;d (DTPMP) 601d under the tradename Deque6t
2066; and ethylene diamine tetrl~methylene phosphonic acld (EDlTEMrA).
The sequestering agents can be used alone or in admixture.
In order to svold 1086 of peroxide bleaching agent, e.g. 60dium
perborate, resulting from enzyme-induced decomposltion, 6uch as by cntDlasc
enzyme, the compositions may sdditlonslly Include an enzyme inhibitor
compound, 1. e . a compound cspable of inhiblting enzyme-induced
decomposition ol the peroxide blesching agent. Suitable inhlbitor compound6
are disclosed in U . S . P . 3, 606, 990"
Of speclsl interest as the Inhibltor compound, mention csn be made ot
hydroxylamine 6ulrate snd other wster-soluble hydroxylamlne 6slt6. In the
preferred nonaqueous composition~ of this Invention, sultable amount6 of the
hydroxylamine salt inhlbilor6 csn be a6 low as sbout 0.01 to 0.4~.
Generslly, however, suitable smounts of enzyme inhibitors sre up to sbout
15~, ~or examp1e, 0.1 to 10~, by welght Or the composltlon.
In addition to the detergent builders, vsrious other detergent additlve6
or sd~uvsnts may be present in the detergent product to give it additiona]
desired properties, either of functionsl or se6thetic nature. Thus, there
may be included In the formulstlon, minor amounts ol 60il suspending or
anti-redeposition sgents, e. g. poly~rinyl slcohol, fatty amides, sodium
carboxymethyl cellulose, hydroxy-propyl methyl cellulose. A preterred
anti-redcposition agent ls sodlum carboxymethyl cellulose ha~rlng a 2 :1 ratlo
of CM/MC which ls sold under the tradenE~rlc Relatin DM ~050.
~ 27
:
~30~46Z
.
Optical brighteners for cotton, polyamide and polyester fabrics can be
used. Suitable optical brighteners include stilbene, triazole and benzidine
sulfone compositions, especially sulfonated substituted triazinyl stilbene,
sulfonated naphthotriazole stilbene, benzidene sulfone, etc., most preferred
are stilbene and triazole combinations. A preferred brightener is Stilben~
Brightener N4 which is a dimorpholine dianilino stilbene sulfonate.
Enzymes, preferably proteo~ytic enzymes, such as subtilisin, bromelin,
papain, trypsin and pepsin, as well as amylase type anzymes, lipase type
enzymes, and mixtures thereof. Preferred enzymes include protease slurry,
esperase slurry and amylase. A preferred enzyme is Esperase SL8 which is
a protease . Anti-foam agents, e . g. silicon compounds, such as Silicane L
7604, can also be added in small effective amounts.
Bactericides, e. g. tetrachlorosalicylanilide and hexachlorophene,
fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet
absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose,
pH modifiers and pH buffers, color safe bleaches, perfume, and dyes and
bluing agents such as ultramarine blue can be used.
The composition may also contain an inorganic insoluble thickening agent
or dispersant of very high surface area such as finely divided silica o2
20 , extremely fine particle size (e. g. of 5-100 millimicrons diameters such as sold
under the name Aerosil) or the other highly voluminous inorganic carrier
materials disclosed in U.S.P. 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; it has been found, for instance, that silica snd silicates promote
the undesired decomposition of the peroxyacid.
In an embodiment of the invention the stability of the builder salts in
the composition during storage and the dispersibility of the composition in
water is improved by grinding and reducing the particle size of the solid
-~ rRf~ 28
::
~i~ 13V046Z
builders to less than 100 microns, preferably less than 40 microns and more
preferably to less than 10 microns. The solid builders, e.g. sod:um
tripolyphosphate (TPP), are generally supplied in particle sizes of about
100, 200 or 400 microns. The nonionic li~uid surfactant phase can be mixed
with the solid builders prior to or after carrying out the grinding operation.
In a preferred embodiment of the invention, the mixture of liquid
nonionic surfactant and solid ingredients is subjected to an attrition type of
mill in which the particle sizeg of the 601id 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) . Preferably legs than about 10%, especially less
thsn about 5~6-of all the suspended particles have particle 6izes greater tharl
10 microns. Compositions whose di6persed particles are of ~uch small size
have improved stability against separation or settling on 6torage. Addition
of the acid terminated nonionic surfactant compound csn decrease the yield
stre6s of such dispersions and sid in the dispersibility of the dispersions
without a corre6ponding decres6e in the disper6ion6 stability against
settling .
In the gr~nding operstion, 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 snother by the nonionic surfactant liquid. After the
grinding step sny remaining liquid nonionic surfactant can be added to the
ground formulation. Mills which employ grinding bslls (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 grinding bslls. 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 be
employed; when using such a mill, it is desirable to pass the blend of
~` ~ 30 nonionic surfactant and solids first through a mill which does not effect such
` 29
:~ : I
~30()4~Z
62301-1439
fine grinding (e.g. a colloid mill) to reduce the particle size
to less than 100 microns (e.g. to about 40 microns) prior to the
step of grinding to an average particle diameter below about 10
microns in the continuous ball mill.
In the preferred heavy duty liquid laundry detergent
compositions of the invention, typical proportions (percent
based on the total weight of composition, unless otherwise
specified) of the ingredients are as follows:
Liquid nonionic surfactant detergent in the range of
about 10 to 60, æuch as 20 to 50 percent e.g. about 30 to 40
percent.
Acid terminated nonionic surfactant may be omitted, it
is preferred however that it be added to the composition in an
amount in the range of about 2 to 20, such a~ 3 to 15 percent,
e.g. about 4 to 10.
Detergent builder, such as sodium tripolyphosphate
(TPP), in the range of about 10 to 50 or 20 to 60, such as 25
to 45 percent, e.g. about 25 to 35.
Alkali metal silicate in the range of about 0 to 30,
such as 5 to 25 percent, e.g. about 10 to 20.
Copolymer of polyacrylate and polymaleic anhydride
alkali metal salt anti-incrustation agent in the range of about
0 to 10, such as 2 to 8 percent, e.g. about 3 to 5.
Alkylene glycol monoalkylether anti-gel agent may be
omitted, it is preferred however that it be added to the com-
position in an amount in the range of about 5 to 20, such as 5
to 15 percent, e.g. about 8 to 12.
~; Higher alkyl sulfonate or higher alkyl poly lower
alkoxy qulfate anti-settling agent in the range of 0.1 to 5,
preferably 0.3 to 2.0 and more preferably about 0.5 to 1.5
~30 ~ percent. It i9 an esqential feature of the invention that at
-30-
~ '
:; .
130~46Z 62301-1439
least one of the higher alkyl sulfonate or higher alkyl poly
lower alkoxy sulfate anti-settling stabilizing agents be
included in the composition.
Phosphoric acid alkanol ester stabilizing agent in the
range of O to 2.0 or 0.1 to 2.0, such as 0.10 to 1.0 percent.
Aluminum salt of fatty acid stabilizing agent in the
range of about O to 5.0, such as O.S to 2.0 percent, e.g. about
0.1 to 1.0 percent.
Bleaching agent in the range of about O to 30, such as
2 to 20, e.g. about 5 to 15 or 8 to 12 percent.
Bleach activator (eg TAED) in the range of about O to
15, such as 1 to 10, e.g. about 2 to 6 percent, especially 3.5
to 5.5 percent.
Sequestering agent for bleach in the range of about O
to 3.0, preferably 0.5 to 2.0 percent, e.g. about 0.75 to 1.25
percent.
Anti-redeposition agent in the range of about O to
3.0, preferably 0.5 to 2.0 percent, e.g. 0.75 to 1.25 percent.
Optical brightener in the range of about O to 2.0,
preferably 0.25 to 1.0 percent, e.g. 0.25 to 0.75 percent.
Enzymes in the range of about O to 3.0, preferrably
0.5 to 2.0 percent, e.g. 0.75 to 1.25 percent.
Perfume in the range of about O to 3.0, preferably
0.25 to 1.25 percent, e.g. 0.75 to 1.0 percent.
Dye in the range of about O to 0.10, preferably
0.0025 to 0.050, e.g. 0.0025 to 0.0100 percent.
Various of the previously mentioned additives can
optionally be added to achieve the desired function of the added
materials.
Mixtures of the acid terminated nonionic surfactant
-~30~ and the alkylene glycol alkyl ether anti-gel agents can be used
~ ~ B -31-
046Z
62301-1439
and in some cases advantages can be obtained by the u~e of such
mixtures alone, or with the addition to the mixture of a
stabilizing and anti-settling agent.
In the selection of the additives, they wilI be chosen
to be compatible with the main constituents of the detergent
composition. In this application, as mentioned above, all
proporations and percentage~ are by weight of the entire formu-
lation or composition unless otherwise indicated.
The concentrated nonaqueous nonionic liquid detergent
composition of the present invention dispenses readily in the
water in the washing machine.
~;2
:~ V
-31a-
~ ~ '
~ 13V046Z
The presently used home washing machines normally use 250 gms of powder
detergent to wash a full load of laundry. In accordance with the present I
invention only 77 cc or 100 gms of the concentrated liquid nonionic detergent ¦
composition is needed.
In a preferred embodiment of the invention the detergent composition of
a typical formulation is formulated using the below named ingredients:
Weight %
Nonionic surfactant detergent. 30-40
Acid terminated surfactant. 4-10
Detergent builder salt. 25-35 .
Copolymer of polyacrylate and polymaleic anhydride alkali 3-5
metal salt anti-encrustation agent (Sokalan CP-5).
Alkylene glycol monoalkylether anti-gel agent. 8-12
Higher alkyl sulfonate sodium salt or higher alkyl 0.5-1.5
poly ethoxy sulfate sodium salt.
Alkali metal perborate bleaching agent. 5-15
Blesch activator ( TAED ), 2.0-6.0
Optical brightener (Stilbene Brightener N4). 0.25-0.75
Enzymes (Protease-Esperase SL8). 0.75-1.25
2 0 Perfume . O . 75-1.0
~ 32
: :
13(1 (~4~Z
The present invention is further illustrated by the following examples.
EX AM PLE
A concentrated nonaqueous liquid nonionic surfactant detergent
composition is formulated from the following ingredients in the amounts
specified .
Weight
Plurafac RA 50 nonionic surfactant . 38 . 0
Acid terminated Dobanol 91-5 reaction product with 6.0
succinic snhydride.
Sodium tri polyphosphate (TPP). 34.0
Diethy]ene glycol monobutylether anti-gel agent. 4.0
C15 Alkyl sulfonate sodium salt (Mersolat H98 C15) . 1. 0
Sodium perborate monohydrate bleaching agent., 9.0
Tetraacetylethylene diamine (TAED) bleach activator. 6.0
Stilbene brightener. 0.8
Protease (Esperase). 1.2
The addition of 1~ of the alkyl sulfonate sodium salt is found to
increase the yield stress of the formulation from about 2 to about 4 Pa. The
viscosity of the formulation is found to remain about the same.
The formulation is ground for about 1 hour to reduce the particle size
of the suspended builder salts to less than 40 microns. The formulated
detergent corr,position is found to be stable and non-gelling in storage and to
have a high detergent capacity.
~ - 130(~4~z-
EXAl~lPLE 2
A concentrated nonaqueous liquid nonionic surfactant detergent
composition is formulated from the follo~ing ingredients in the amounts
specified .
Weight %
Plurafac RA 50 nonionic surfactant . 36 . 0
Acid terminated Dobanol 91-5 reaction product with 6 . 0
succinic anhydride.
Sodium tri-polyphosphate (TPP). 32.0
Diethylene glycol monobutylether anti-gel agent . 8 . 0
Higher alkyl poly ethoxy ether sulfate sodium salt. 1.0
Sodium perborate monohydrate bleaching agent. 9 .
Tetraacetylethylene diamine (TAED) bleaching agent. 5.0
Stilbene brightener. 0.75
Protease (Esperase). 1.25
Perfume . 1. 0
The formulation is ground for about one hour to reduce the particle
size of the suspended builder salts to less than 40 microns. The formulated
detergent composition is found to be stable and non-gelling in storage and to
have a high detergent capacity.
The formulations of Examples 1 and 2 can be prepared without grindinE
the builder salts and suspended solid particles to a small particle size, but
best results are obtained by grinding the formulation to reduce the particl~
size cf the suspended solid particles.
The builder salts can be used as provided or the builder salts and
suspended solid particles can be ground or partially ground prior to mixin
them with the nonionic surfactant. The grinding can be carried out in part
prior to mixing and grinding completed after mixing or the entire grinding
operation can be carried out after mixing with the liquid surfactant. Th~
I - 13()~46Z
formulations containing suspended builder and solid particles less than 40
microns in size sre preferred.
It is understood that the foregoing detailed description is given merely
by way of illustration and that variations may be made therein without
S de a ting o the spirit of the invention.
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