Note: Descriptions are shown in the official language in which they were submitted.
13~66~5
62301-1437
HIGH FOAM NONAQUEOUS LIQUID NONIONIC
LAUNDRY DETERGENT COMPOSITION AND METHOD OF USE
BACKGRQUND OF~ THE INVENTION
(1) Field of Invention
This invention relates to nonaqueous liquid fahric
treating compositions. More particularly, this invention
relates to high foam nonaqueous liquid laundry detergent
compositions which are stable ayainst phase separation and
gelation and are easily pourable and to the use of these
compositions ~or cleaning soiled fabrics.
(2) Discussion of Prior Art
Liquld nona~ueous heavy duty laundry detergent
compositions are well known in the art. For lnstance,
compositions of that type may comprise a liquid nonionic
surfactant ln which are dispersed particles of a builder, as
shown 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 r 040 and
1,600,981.
The related Canadian appllcations assigned to the
common assignee are 498,815 filed December 31, 1985; 478,380,
~iled April 4, 1985; and ~78~379r filed April 4, 1985.
These applications are directed to liquid nonaqueous
nonionic laundry detergent compositions.
Liquicl detergents are o~ten considered to be more
convenlent to employ than dry powdered ox particulate products
and, therefore, have found substantial favour with consumers.
They are readlly measurable, speedily dissolved in the wash
.
water, capable of being easily applied in concentra~ed
; solutions or dispersions to soiled areas on garments to be
laundered and are non-dusting, and they usually occupy less
storage space. Additionally, the liquid detergents may have
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62301-1437
incorporated in their formulations materials which could not
stand drying operations without deterioration, which materials
are
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oflen desirably employed in the m~lnuf.lcture of particulate detergcnt
products. Although they are possessed of many advantages over uni~ary or
particulate solid products, liquid detergents often have certain inherent
disadvantages too, which have to be overcome to produce acceptab]e
commercial detergent products. Thus, some such products do not readily
foam, separate out on storage and others separate out on cooling and are no~
readily redispersed. In some cases the product viscosity changes and it
becomes either too thick to pour or so thin as to appear watery. Some c]ear
products become cloudy and others gel on standing.
10The present inventors have been involved in studying the behavior of
nonionic Iiquid surfactant systems with particulate matter suspended therein.
Of particular interest has been nonaqueous built laundry liquid detergent
compositions and the problem of settling of the suspended builder and other
]aundry additives as uell as the prob]em of gelling associated with nonionic
15surfactants. These considerations have an impact on, for example, product
stability, pourability and dispersibility.
It is known that one of the major problems with built liquid laundry
detergents is their physical stability. This problem stems from the fact that
the density of the so]id particles dispersed in the nonionic liquid surfactant
20 ~is higher than the density of the liquid surfactant~
Therefore, the dispersed particles tcnd to settle out. Two basic
solutions e~ist to solve the settling out problem: incrcase nonionic liquid
viscosity and rcduce the dispersed solid particle size.
It is kno~vn that suspensîons can be stabilized against settling by
; 25adding inorganic or organic thickening agents or dispersants, such as, for
example, very high surfnce area inorganic materials, e. g. finely divided
silica , clays , etc ., organic thickcners ; such as the cellulose ethers , acrylic
and ocrylamide polymers, polyelcctl olytes, etc. Howe~rer, such increases in
susp~nsion viscosity are nntur.llly limited by the requirement that the liquid
suspension be rendily pourable and flo~able, c~Ten at low tcmpclature
~ 3
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Furth~rn~ore, thcse ad(litives do not contlibute to ~e clcaning perforrnallce
of the formulation.
Grinding to reduce the partic]e size provides the fo]lowing advant~ges:
1. Specific surface area of the dispersed particles is increased, and,
therefore, particle wetting by the nonaqueous vehicle (liquid nonionic) is
proportionately improved.
2. The average distance between dispersed particles is reduced with a
proportionate increase in particle-to-particle interaction. Each of these
effects contributes to increase ~he rest-gel strength and the suspension yield
stress while at the same time, grinding signiIicantly reduces plastic
viscosity.
The yield stress is defined as the minimum stress necessary to induce a
plastic deformation (flow) of the suspension. Thus, visualizing the
suspension as a loose network of dispersed particles, if the applied stress is
lo~er than the yield stress, the suspension behaves like an elastic gel and
no plastic flow will occur. Once the yield stress is overcome, the network
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
~; 20 viscosity decreases. Finally, if the ~shear stress is much higher than the
y~eld stress value, the dispersed particles are completely shear-deflocculatcd
and the apparent viscosity is very low, as if no particle interaction ~vere
present.
~; Therefore, the higher the yleld stress of the suspension, the higller
2S the apparent viscosity at low shear rate and the better is the physical
stability against settling of the prodact.
In addition to the problem ;of settling or phase separation, the
; nonaqueous liquid laundry detergents based on liquid nonionic surfactants
~uffer frvm the dra~vback that the nonionics do llOt rcadily produce a stal>le
30 ~ foam and they tend to gel ~vhcn added to cold water. This is a palticu!ally
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important prob]em in the ordinary use of European llousehold autom~tic
~-ashing machines where the user places the laundry detergent composition in
a dispensing unit (e. g. a dispensing dra~er) of the machine. During the
operation of the machine the detergent in the dispenser is subjected to a
S Stl eam of cold uater to transIer it to the 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 during operation of the machine,
and a deposit OI the composition builds up with repeated wash cycles,
eventually requiring the user to ilush tbe dispenser with hot water.
The gelling phenomenon can also be a problem whenever it is desired to
c arry out ~-ashing using cold water as may be recommended for certain
synthetic and delicate fabrics or fabrics which can shrink in warm or hot
wster.
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
transyortation vehicles.
Partial solutions to the gelllng problem in aqueous substantially
builder-free compositions have been proposed and Include, for example,
dilutillg the liquid nonionic Yith certain~ viscosity controlling solvents and
~ gcl-inhibit~ng agents; such as lower alkanols, e.g. ethyl alcohol (see U.S.P.
; 3,~53,380), alkali metal formates~ and adlpates (see~ U.S.P. 4J368,147),
~ hexylene glycol, pol~,~ethylene glycol,~eic. and nonionic structure modi~ication
and optlmization.
;Improvements are dcsircd in the production of a stable îoam, and in the
stability and gel inllibition of nonaqu~ous liquid fabric treating compositions.
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62301-1437
BRIBF DESCRIPTION OF THE INVENTION
In accordance with the present lnvention a high foam,
highly concentra~ed stable nonaqueous liquid laundry detergent
composition is prepared by adding to the compositlon a~ the
main nonionic surfactant component a Cg-Cll fatty alcohol
ethoxylated by 5 moles of ethylene oxide per mole of alcohol.
The compositions of the present invention contain as
~- an essential ingredient and as the major constituent of the
liquid nonionic surfactant component of the composition a
Cg-Cll fatty alcohol ethoxylated by 5 moles of ethylene oxide
per mole of alcohol. The Cg-Cll alkyl (C2H2-O)5OH nonionic
surfactant of the present invention will comprise about 50 to
100~ of the nonionic surfactant component o~ the composition,
e.g. 50 to 90%, such as 50 to 75% of the nonionic component.
In order to improve the viscosity characteristics of the
; composition and the storage properties of the compositlon there
can be added to the composition viscosity improving and anti- '
gel agents such as alkylene glycol mono alkyl ethers and anti-
settling agents such as phosphoric acid alkanol ester. In
preferred embodiment of the invention the detergent composition
contains an alkylene glycol mono alkyl ether and a phosphoric
` acid alkanol ester anti-settling stabilizing agent. Acid
; ~ terminated nonionic surfactant anti gel agents, e.g., those
disclosed in the Canadian application Ser. No. 478,3~0, filed
Aprli~4,~1985, are not added to the oomposition becau e they
are believed to form with the calcium ions present in the wash
l1quor a~calcium salt which is a~foam lnhibitor.
Sanitizing or bleaching agents and activators
therefor can be added to improve the bleaching and cleanslng
characteristics of the composition.
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62301-1437
In an embodiment of the invention the builder
components of the composition are ground to a particle size of
less than 100 microns and to preferably less than 40 microns ~o
further improve the stability of the
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suspe]lsiGn of the builc'cr compol~c-nts in the liquid nonionic surfactant
detergent .
In addition other ingredients can be added to the composition such as
anti-incrustation agents, allti-foam agents, optical brighteners, enzymes,
anti-redeposition agents, perfume and dycs.
Accordingly, in one aspect the present invention provides a liquid
heavy duty laundry composition composed of a suspension of a detergent
builder salt, e. g. a phosphate bui~der salt, in a liquid nonionic surfactant
wherein the composition includes as the main nonionic component a high foam
producing Cg-Cll fatty alcohol ethoxylated by 5 moles of ethylene oxide per
mole of a]cohol, which composition produces high foam, is stable against
settling and is readily dfspersible in wat~r.
According to another aspect, 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
into the u ashing machine and are readily dispersible in water.
Accordin g to another aspect, the invention provides a method for
dispensing a high foam Cg-Cll alkyl (C2H2O)5OH liquid nonionic laundry
detergent composition Into and/or l~ith cold water tYithout undergoing
` gelation,
ADVANTAGES OVER THE PRIOR ART
The use of the high foam Cg-Cll alkyl (C2H2O)5OH nonionic surfactant
as ~ the main component of the nonlonic surfacfant in the compositions
produces a high foaming detergent composition without the need to add
specific foaming agents.
The concentrated nonaqueous liquid nonionic surfactant laundry
detergent compositions of the present~ invcntion have the advantages of bcing
stab]e, non-settling in storage, and non-gclling in storage. The liquid
30 ~ cGmpositi(>ns are easily pourable~ casily measured and easily put into the
laull~ry uaslling machincs and are readily dispersible in ~ater.
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62301-1437
AIMS OF THE_INVENTION
The present invention seeks to provide a high
foaming, stable liquid heavy duty nonaqueous nonionic detergent
composition containing an anti-settling stabilizing agent and
an anionlc phosphate detergent builder salt suspended in a
nonionic surfactant.
The invention also seeks to provide a high foam
liquid fabric treating compositions which are suspensions of
insoluble inorganic particles in a nonaqueous liquid and which
are storage stable, easily pourable and disperslble in cold,
warm or hot water.
This invention also seeks to formulate a high foam
built heavy duty nonaqueous liquid nonionic ~urfactant laundry
detergent compositions which can be poured ak 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 durlng the winter
months.
This invention further seeks to provide a high foam,
non-gelling, stable suspensions o~ heavy duty buil~ nonaqueous
liquid nonionic laundry detergent composition which includes as
the maln~nonionic surfaotant component constituent a Cg-Cll
~alkyl ~CH2CH2O)5OH nonlonia surfactant. ~ -
Tha invention will become~more apparen~ from the
followlng detaIled description of preferre~d embodiments and is
gen:erally provided for by preparing a detergent composition by
adding to the nonaqueous liquid nonionic surfactant a high foam
Cg to Cll alkyl ~CH2CH2O)5OH nonionlc surfactant, wherein said
composition includes inorganic or organic fabric ~reating
~addltlves, e.g. viscosity lmproving agents and one or more
anti-gel~agents, anti-incrus~ation agents, pH control agents,
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62301-1437
bleaching agenks, bleach activators, anti-foam agents, optical
brighteners, enæymes, anti-redeposition agents, perfume and
dye~.
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DETAILED DESCRlPTlO~' OF Tl~E ;N~'EhlTION
In accordance with the present invention the foaming properties of the
- nonaqueous liquid nonionie laundry detergent composition is substantially
improved by the addition of Cg-Cll alkyl (CH2CH2O)5O~ nonionie surfactant
to the composition.
The addition of C9-C11 alkyl (CH2CT~2O)~OH as the major eonstituent of
the nonionic surfactant component of the composition substantially improves
the foamin~ properties of the composition. The eompositions of the present
invention eontain as an essential ingredient the Cg-Cll alkyl (CH2CH2O)5OH
as the main constituent of the nonionic surfactant component of the
composition.
The Cg-Cll alkyl (CH2CH2O)5OH nonionie surfaetant is available from
~hell Chemical Company, Ine. under the Dobanol 91-5 trademark.
I~'onionie Surfactant Detergent
Nonionic synthetie organie detergents that can be employed in small
amounts in the practice of the invention may be any of a wide variety of
known compounds.
As is ~vell known, the nonionie synthetie organie detergents are
ehflractel ized by the presence of an organie hydrophobie group and an
org~nic hydrophilic gl'OUp and are typically produeed by the condensation of
an~ organie aliphatic or alkyl aromatio hydrophobie compound with ethylene
o xide (hydrophilie in natule). Practic~l:ly any hydrophobie eompound having
a carboxy, hydroxy, amido or amino group ~vith a free hydrogen nttaehed to
the nitrogen ean be eondensed t~ith ethylene oxide or with the polyhydration
product thereof, polyethylene glycol, ~to form a nonionie detergent. The
longth of~ the h~drophilie or polyoxy ethylene ehain ean be readily adjusted
to ~ aehieve the dcsired balanee between the hydrophobie and hydrophilie
groups. Typical suitablA nonionie surfactants are those disclosed in U.S.
patents 4,316,812 and 3,630,929.
Usually, tile rlonic~ic detergents are poly-lo~er allcoxylated lipophiles
; ~ ~ ~rhcrcln the desired hydlophile-lipophile balance is obtained from addition of
1 ~3~66~
a hydrophiIic poly-lov.er alkoxy group to a liI,opnilic moiety. A preferred
class of the nonionic detergent employed is the poly-]ot~er aIkoxylated higher
alkanol wherein the a]kanol 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
which contain from 6 to 8 or 5 to 9 lower alkoxy groups per mol.
Preferably, the lower alkoxy is ethoxy but in some instances, it may be
desirably mixed with propoxy, the latter, if present, often being a minor
(less than 50~) proportion.
Exempla'ry 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. ~eodol ~25-7 and Neodol 23-6 . 5, which produc~s are made by Shell
Chemjcal Company, lnc. The fc-rmer 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 examp]es of such detergents include Tergitol 15-S-7 and Tergitol~
15-5-9, both of which are linear secondary alcohol ethoxylates made by
Union Carbide Corp. The former ls~ mixed ethoxylation product of 11 to 15
carbon atoms l;near secondary alkanol with seven mols of ethylene oxide and
the latter is a similar product but with nine mols of ethylene oxide being
Z5 reacted.
Also useful in the present composition as a component of the nonionic
- detergcnt are higher Inolecular weight nonionics, such as Neodol 45-11,
which are simi]ar ethylene oxide condensation products of higher fatty
alco}lols, with the higher fatty alcohol being of 14 to 15 carbon atoms and
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the number of ethylene oxide groups per mol being about ll. Such products
are also made by Shell Chemical Company.
Other useful nonionics are represented by the commercially well known
c]ass of nonionics so]d 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 propy]ene
oxide, terminated by a hydroxyl group. Examples include products which
are (A) C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3
moles propylene oxide, (B) Cl3-C15 fatty alcohol condensed with 7 mo]es
propylene oxide and 4 moles ethylene oxide, (C) C13-C15 fatty alcohol
condensed with 5 moles propylene oxide and 10 moles ethylene oxide, and
(D) which is a l :1 mixture of products (B) and (C) .
Another group of liquid nonionics are commercially available from Shell
Chemical Company, Inc. under the Dobanol trademark, e. g. Dobanol 25-7
which is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles
ethylene oxide per mole of fatty alcohol.
Another useful group of nonionic surfactants are the "Surfactant T"
series of nonionics availabe from British Petroleum. The Surfactant T
nonionics are obtained by the ethoxylation of secondary C13 fatty alcohols
having a narrow etllylene oxide distribution. The Surfactant T5 has an
average of 5 moles of ethylene oxide; Surfactant T7 an average of 7 moles of
ethytene oxide; Surfactant T9 an average of 9 moles OI ethylene oxide and
Surfactant T12 an avelage of 12 ~ moles of ethylene oxide per mole of
secondary Cl3 fatty alcohol. _
In the compositions of this invention, useful nonionic surfactants
include the C12-C15 secondary fatty alcohols with relatively narrow contents
of ethylene oxide in the range of from about 7 to 9 moles, and the C9 to C11
fatty alcohols ethoxylated ~vith about 5-6 moles ethylene oxide,
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I\iixtures of two or more of the licluid nonionic surfactants can be used
with the high foam Cg-Cll alkyl (CH2CH20)50H surfactant of the present
invention and in some cases advantages can be obtained by the use of such
mixtu res .
BUILDER SALTS
The liquid nonaqueous nonionic surfactant used in the compositions of
the present invention has dispersed and suspended therein fine partic]es of
inorganic and/or inorganic detergent builder salts.
The invention detergent compositions include water soluble and/or water
insoluble detergent builder salts. Water soluble inorganic alkaline builder
s~lts which can be used alone with the detergent compound or in admixture
with other builders are alkali metal carbonates, bicarbonates, borates,
phosphates, polyphosphatcs, and silicates. (Ammonium or substituted
ammonium snlts can also be used. ) Specific examples of such sa]ts are
; 15 sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium
pyrophosphate, potàssium 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 th~s invention are generally highly
co~lcentrated, and, therefore, may be used at re]atively low dosages, it is
desirable to supplement any phosphate builder (such as sodium
~; ~ripo]yphosphate) with an auxiliary builder such as a poly lo-ter carboxylic
acid or a ~>olymeric carboxylic acid having high calcium binding capacity to
inhibit incrustation which could other~vise be caused by ~ormation of an
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insoluble calcium phosphate.
A suitable lower poly carboxylic acid comprises alkali metal salts of
lo~ver polycarboxylic acids, preferably the sodium and potassium saits.
Suitable lower pol~carboxylic acids have t~vo to four carboxylic acid groups.
30 ~ The p~ efcrred sodium and potassium lower polycarboxylic acids salts are the
citric and tartaric acid salts.
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62301-1437
The sodium citric acid salts are the most preferred,
especially the trisodium ci~rate. The monosodium and disodium
citrates can also be used. The monosodium and disodium
tartaric acid ~alts can also be used. The alkali metal lower
polycarboxylic acid salts are particularly good builder salts;
because of their high calcium and magnesium binding capacity
they inhibit encrustation which could otherwise be caused by
forma~ion o~ insoluble calcium and magnesium salts.
; Qther organic builders are polymers and copolymers of
polyacrylic acid and polymaleic anhydride and the alkali metal
salts thereo~. More specifically such builder salts can
consist of a copolymer which is ~he reaetion product of about
equal moles of methacrylic acid and maleic anhydride which has
been completely neutralized to form the sodlum salt thereof.
The builder is commercially available under the trademark of
Sokalan CP5. This bullder serves when used even in small
amounts to lnhlbit encrustation.
Examples o~ organic alkaline sequestrant builder
salts whlch can be used with the detexgent builder salts or in
admixture wlth other organic and inorganic builders are alkali
metal, ammonium or substituted am~onlum, aminopolycarboxylates,
e.g. sodium and potassium ethylene diaminetetraacetate ~EDTA),
sodium;and potassium nitrilotriacetates (NTA), and
~; ~ triethanolammonium N-(2-hydroxyethyl)nitrilodiaceta~es. Mixed
sal~ts o~these aminopolycarboxylates are also suitable.
Other suitable builders o~ the organic type include
car~oxymethylsuccinates, tartronates and glycollates. Of
speaial value are the polyacetal carboxylates. The polyacetal
carboxylates and their use in deterg~nt compositions are
30~ described in Canadian application No. 516,256, filed ~ugust 19,
1986, a~signed to applicants' assignee and in a U.S.P. Nos.
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62301-1437
4,1~4,226, 4,315,092 and 4,146,495.
The alkali metal silicates are useful builder salts
which also function to adjust or control the pH to make the
composition anticorrosive to washing machine parts. Sodium
silicates of Na2O/SiO2 ratlos of from 1.6/1 to 1/3.2,
especially about 1/2 to 1/2.8 are preferred. Potassium
silica~es of the same xatios can also be used.
Other typical suitable builders include, for example,
those diselosed in U.S. Patents 4,316,812, 4,264,466 and
3,630,929. The inorganic builder salts can be used with the
nonionic surfac~ant detergent compound or in admixture with
other inoryanic bullder salts or with organic builder salts.
The water insoluble crystalline and amorphous
aluminosilicate zeolltes can be used. The zeolites generally
have the formula
(M2)X- (A123)y~ (Sio2)z.wH2o
wherein x is l, y is from 0.8 to 1.2 and preferably l, z is
~rom 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0
to 9, preferably 2.5 to 6 and M is preferably sodium. A
typical zeolite is type A or slmilar structure, with type 4A
partlcularly preferrad. The preferred aluminosiliaates have
calclum ion exchange capacities of about 200 milliequivalents
per gram~or greater, e.g. 400 meq lg.~
Various crystalline zeolites (i.e. alumino-silicates)
that can be used are described in Britl~sh Patent 1,504,168,
U.S.P.~4,~409,136 and Canadian Patents 1,072,835 and 1,087,477.
An example of amorphous zeolltss useful herein can be found in
Belglum Patent 835,351.
Other materlals such as clays, partlcularly of the
water~insoluble types, may be useful ad~uncts in compositlons
of this inventlon. Partiaularly use~ul is bentonite. This
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62301-1437
material is primarily montmorillonite which is a hydrated
aluminum silicate in which about 1/6th of the aluminum atoms
may be replaced by magnesium atoms and with which varying
amounts of hydroyen, sodium, po~assium, calcium, etc., may be
loosely combined. The bentonite in its more purified form
(i.e. free from any grit, sand, etc.) suitable for detergents
contains at least 50% montmorillonite and thus its cation
exchange capacity is at least about 50 to 75 meq per lOOg of
bentonite. Particularly
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preferred bentonitcs are the l~'~on~ing or ~'cstcln U.S. bentonites t~hich h~e
been sold as Thixo-jels~1, 2, 3 and 4 by Georgia KaGlin Co. These
bentonites are known to soften textiles as described in British Patent 401,413
to 1\1arriott and British Patent 461, 221 to l\~arriott and Guan .
Viscosity Control and Anti Gel Agents
The inclusion in the detergent composition of an effective amount of low
molecular weight amphiphilic compounds which function 8S Yiscosity control
and gel inhibiting agents for the nonionic surfactant substantially improves
the storage properties of the composition. The viscosity control and gel
inhibiting agents act to lower the temperature at which the nonionic
surfactant will form a gel when added to water. Such viscosity control and
~` gel inhibiting agents can be, for example, low molecular weight ~kylene
oxide lower mono-alkyl ether amphilic compounds. The amphiphilic
compounds can be considered to be analagous in chemical structure to the
ethoxylated and/or propoxy]ated fatty alcohol liqlLid 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 amphipllilic compounds are represented by the following general
formula
~2
1 R O ( C H C H2O)nH
~here R is a C2-C8 alkyl group, R is hydrogen or methyl and n is a
number of from about 1 to 6, on average.
Specifically the compounds~ are lower (C2 to C3) alkylene glycol mono
¦~ io~ver (C2 to C5) alkyl ethers.
l~iore specificaHy the compounds are mono-, di- or tri- lower (C2 to C3)
alkylcne gïycol mono lo~ver (Cl to C5~ alkyl ethers.
Specific exnmples of suitable amphiphilic compounds include
ethylclle glycol monoetllyl ether C2H5-O-CH2CH2QH,
(lietilylcne glycol mollobutyl cthcr C4119-O-ICH2CH2O)2H,
tctraethylene glycol monobutyl cther C4H7-O-(CH2CH2O)4H and
6 ~R/~ 15
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62301-1437
dipropylene glycol monomethyl ether CH3-0-(CHCH20)2H.
CH3
Die~hylene glycol monobutyl ether is especially
preferred and is supplied by Dow Chemical Co. under the
trademark Do~-anol DB.
Another suitable viscosity control and gel inhibiting
ayent supplied by Dow Chemical Co. that can be used is Dowanol
PIB-T, which is a mix~ure of mono-, di- and tripropylene glycol
monomethyl ether.
The inclusion in the composition o~ the low molecular
weight lower alkylene glycol mono alkyl ether decreases the
viscosity of the composition, such that it is more easily
pourable, improves the stability against settling and improves
the dispersibility of the composition on the addition to warm
water or cold water.
The compositions of the present invention have high
foam properties, improved viscosity and stability
characteristics and remain stable and pourable at temperatures
as low as about 5C and lower.
In an embodiment of this invention a small amount of
a stabilizing agent which is an alkanol ester of phosphoric
; acid aan be added to the formulation. Improvements in
stability of the composition may be achieved by incorporation
~; of a small effective amount of~an acidic organic phosphorus
compound having an acidlc - POH group, such as a partial ester
of phosphorous acid and an alkanol. As disclosed in the
:; ~ commonly aæsigned Canadlan application Serial No. ~78,379 filed
April 4, 1985, the acidic organic phosphorous compound having
an acidic - POH group can increaæe the stability of the
suspension of builders in the nonaqueous liguid nonionic
suxfactant. The acidic organic phosphorus compound may be, for
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~ ~ ~ 16
~ ~3~ 5~
~ 2301-1437
instance, a partial ester of phosphoric acid and an alcohol
such as an alkanol which has a lipophilic character, having,
for instance, more than 5 carbon atoms, e.g. 8 to 20 carbon
atoms.
A specific example is a partial ester of phosphoric
acid and a C16 to C18 alkanol (~mpiphos 5632 ~rom ~archon~; it
is made up of about 35~ monoes~er and 65% diester.
The inclusion of quite small amounts, e.g. 0.3% by
weight of the acidic organic phosphorus compound makes the
suspension stable against se~tling on standing but remains
pourable, while, for the low concentra~ion of stabilizer i~s
plastic viscosity will generally decrease. The addltion of
more than about 0.3%, e.g. about 1.0% or more is avoided since
the higher concentratlon of organic phosphorous ester would be
expected to inhibit foam.
Bleachinq~A~ents
The bleaching agents axe classified broadly, for
convenience, as chlorine bleaches and oxygen bleaches.
Chlorine bleaches are typified by sodium hypochlorlte (NaOCl,
~0 potassium dischloroisocyanurate (59% available chlorine), and
trichloroisocyanuric acid (~5% available chlorine). Oxygen
bleaches are preferred and are represented by percompounds
wh1ch l~iberate hydrogen~peroxide in solution. Preferred
examples include sodium and potasKium perborates,
percarbonates, and perphosphates, and potassium monopersulfate.
The perborates, particularly sodlum perborate monohydrate, are
e~pecially preferred.
; ~ The peroxygen compound is preferably used in
admixture~with an activator therefor. Suitable activators
which can lower the ef~ective operatlng temperature of the
peroxide bleaching agent are disclosed, for example, in U.S.P.
17
;,
~3~16fiS~
62301-1~37
4,264,466 or in column 1 of U.S.P. 4,430,244. Polyacylated
compounds are preferred activators; among these, compounds such
as tetraacetyl ethylene diamine ~"TAED") and pentaacetyl
qlucose are particularly preferred.
Other useful ac~ivators include, for example,
acetylsalicylic acid derivatives, ethylidene benzoate acetate
and its salts, ethylidene carboxyla~e acetate and its salts,
alkyl and alkenyl suacinic anhydride, tetraacetylglycouril
("TAGU"~, and the derivatives of these. Other useful classes
of activators are disclosed, for example, in U.S.P. ~,111,826,
4,422,~50 and 3,661,789.
The bleach activator usually interacts with the
peroxygen compound to form a peroxyacid bleaching agent in the
wash water. It is preferred to include a sequestering agent of
high complexing power to inhibit any undesired reaction between
such peroxyacid and hydrogen peroxide in the wash solution in
the presence of metal ions.
Suitable sequestering agents for this purpose include
the sodium ~alts of nitrilotriacetic acid (NTA), ethylene
diamlne tetraacetic acid (EDTA), diethylene triamine
pentaacetic aaid (DETPA), diethylene triamine pentamethylene
phosphonlc acid (DTPMP~ sold under the trademark Dequest 2066;
and ethylene dlamine tetramethylene phosphonic acid (EDITEMPA).
The sequestering agents can be used alone or in admixture.
In order to avoid loss o~ peroxide bleaching agent,
e.g. sodium perborate, resultin~ from enzyme-induaed
decomposition, such as by catalase en~ymet the compositions may
addltionally include an enzyme inhibitor compound, i.e. a
~; ~ aompound capable of inhibiting enzyme-induced decomposition of
the peroxide bleaching agent. ~uitable inhibitor compounds are
di~closed in U.S.P. 3,506,990.
i 18
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62301-1437
Of special interest as the inhibitor compound,
mention can be made of hydroxylamine sulfate and other water-
soluble hydroxylamine salts. In the preferred nonaqueous
compositions of this invention, suitable amounts of the
hydroxylamine salt inhibitors can be as low as about 0.01 to
0.4%. Generally, however, suitable amounts of enzyme
inhibitors are up to about 15%, for example, 0.1 to 10%, by
weight of the composition.
In addition to the detergent builders, various other
detergent additives or adjuvants may be present in the
detergent product to give it additional desired properties,
elther o- iunc~1onal or aesthetic nature. Tùus, ~here
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13~fi65~
may be included in the fo~ r,ullation, minor amounts of soil suspending or
anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium
carboxymethyl cellu]ose, hydro~;y-propyl methyl cellulose. A preferred
anti-redeposition agent is sodium carboxymethyl cellu]ose having a 2 :1 ratio
of CMC/I~C which is sold under the tra~l-a~ Relatin DM 4050.~
There may also be included in the composition small amounts of Duet$'787
which is a fragrance, i. e. perfume j ~nd which is supplied by Internationpl
Elavors and Fragrances, Inc., Union Beach, NJ 07735. The Duet 787 can be
added in amounts such as 0 to 3, preferably 0.2 to 3 percent, e.g. 0.5 to 2
percent, such as 0.3 to 1.5 percent by weight of the composition.
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 Stilbene
Brightener N4 which is a dianilinodimorphalino stilbene polysulfonate.
Enzymes~ preferably proteolytic enzymes, such as subtilisin, bromelin,
papain, trypsin and pepsin, as t~ell as amy]ase type anzymes, lipase type
enzymes, and mixtures thereof can be added. Preferred enzymes include
protease slurry, esperase slurry and amylase. A preferred enzyme is
Esperase;~SL8 ~vhich is a proteolytic enzyme. Anti-foam agents, e. g. silicon
compound, such as Silicane~1 760~, which is a polysiloxane can also be
added in small effective amounts.
Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene,
fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet
absorbers, anti-yello~ing agents, such as sodium carboxymethyl cellulose,
pH modifiers and pH buffers, color safe blcaches, perfume, and dyes and
bluing agents such as ultramarine blue can be used.
In an embodiment of the invention the stability of the builder salts in
the composition duling storngc and the dispersibility of the composition in
19
^ ~L3~i6~ -
~-ater is imE~loved by grinding and reducing the particle size of the solid
bui]ders to less than 100 microns I preferably less than 40 microns and more
prefera~ly to less than 10 microns. The solid bui~ders, e.g. sodium
tripol~p~osphate (TPP), are generally supplied in particle sizes of about
100, 200 or 400 microns . The nonionic liquid 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 sizes of the solid ingredients are reduced to less
than abowt 10 microns, e.g. to an average particle size of 2 to 10 microns or
even lower (e. g. 1 micron) . Preferably less than about 10%, especially less
than about 596 of all the suspended particles have particle sizes greater than
10 microns. Compositions whose dispersed particles are of such small size
have improved stability against separation or settling on storage. Addition
of the acid terminated nonionic surfactant compound can decrease the yield
stress of such dispersions and aid in the dispersibility of the dispersions
without a corresponding decrease in the dispersions stability against
settling .
In the grinding operation, it is preferred that the proportion of solid
ingred~ents 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. After the
;~ ~grlnding step ~any remaining l~quid nonion~c surfactant can be added to the
~ ground formulation. I\lllls which employ grinding balls (ball mills) or similar
25~ ~ ~ mobile grinding elements have given very ~good results, Thus, one may use
a lnboratory batch attritor having 8 mm di~ameter steat;te grinding balls. ~or
,~
larger scale work a continuously operating mill in which there are 1 mm or
i,5; mm diameter grinding balls working iD a very small gap between a stator
and a rc)tor operating at a rclntively high speed ~e.g. a CoBall mill) may be
cmp~oyed; ~vhen USillg such a mi]l, it is desirable to pass the blend of
, ~ ~
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nol~ionic sl~rf~3ctc~nt and so]i-ls first through a mill ~hich does not effect such
fine grinding (e.g. a col]oid 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
a~er(~ge partic]e diameter belo~ about 10 microns in the continuous ball mill.
S In the preferred heavy duty liquid laundry detergent compositions of
; ~ the invention, t~pical proportions (percent based on the total weight of
composition, unless other~vise specified) of the ing~redients are as follows:
Liquid Cg-Cll alkyl (CH2CH2O)5OH nonionic surfactant detergent in the
range of about 10 to 60, such as 20 to 60~ percent, e.g. about 30 to 45
10 ~ percent.
Detergent builder, such as sodium tripolyphosphate (TPP), in the range
of about 10 to 60, such as 15 to 50 percent, e.g. about 25 to 35 percent.
Alka~i metal silicate in the range of about 0 to 30, such 8S 5 to 25
percent, e. g. about 10 to 20 percent.
Copolymer of polyacrylate and polymaleic anhydride alkali metal salt,
e. g. Sokalan CP5, anti-incrustation agent in the range of abou~ 0 to 10,
such as 2 to 8 percent, e.g. about 3 to 5 percent.
Alkylene glycol m(rloalkylether anti-gel agent in an amount in the range
of 0 to 30, preferably about 5 to 30, such as 5 to 20 percent, e.g. about 5
to 15 percent .
Phosphoric acid alkanol ester stabilizing agent in the range of 0 to 0.75
or O~. l lo 0 . 5, such as 0, 20 to 0 . 5 peroent . ~
Bleaching agent in the range of about 0 to 30, such as 2 to 20, e.g.
~about 5~to 15 percent. ~
25~ ~ Bleach activator in the range ~of~ about 0 to 15, such as 1 to 8, e.g.
about 2~io G percent. ~ ~
~ Sequesteling agent for bleach,~ e.g. Dequest 2066, in the range of
about 0 to 3 . 0, preferably 0 . 5 to a, o percent, e . g. about 0 . 75 to 1. 25
pcrccnt. ~
Anti-rc~leposition ~gent, e. g. Reiatin DM 4050, in the range of about 0
to 4.0, prcfer~bly 0.5 to 3.0 percent, eg. 0.5 to 1.5 percent.
~` ~3~66S~
Optical brightener in the range of about 0 to 2.0, preferably 0.05 to
1. 0 percent, e . g. 0 .15 to 0 . 75 percent .
En z~mes in the range of about 0 to 3 . 0, preferrably 0 . 5 to 2, 0 percent,
e . g. 0 . 75 to 1. 25 percellt .
Perfume in the range of about 0 to 3 . 0, preferably 0 .10 to 1. 25
percent, e . g. 0 . 25 to 1. 0 percent .
Various of the previously mentioned ~dditives can optionally be added to
achieve the desired function of the added materials.
The Cg-Cll alkyl (CH2CH2O)5OH nonionic surfactant is preferably use
with the alkylene glycol mono-eth~r viscosity control and anti-gel agents. In
some cases advantages can be obtained by using both the alkylene glycol
mono-ethers and the phosphorlc acid alkanol ester stabilizers.
In the selection of the additives j they will be chosen to be compatible
with the main constituents of the detergent composition. In this application,
1~ as mentioned above, all proportions and percentages are by weight of the
entire formulation 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.
The presently used home washmg machines normally use 200 to 250 gms of
powder dctergent to wash a full load of laundry. In accordance with the
presellt invention only 78 cc or 100 gms of the concentrated liquid high foam
nonionic detergent composition is needed.
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- -
In an embodiment of ~he illvcntioll the detcrgellt composit;on of a typical
formulation is formulated using the below named ingredicnts:
l~eight %
Cg-Cll alkyl (CH2cll2o~5oH~ 30-45
Phospl~ate detergent builder salt. 10-60
Anti-incrustation agent. 0-l0
Alkylene glycol monoalkylether anti-gel agent. 5-15
~ Phosphoric Acid Alkanol Ester. 0 . 2-0 . 5
; ~ ~ ~ Anti-redeposition agent . 0-4 . 0
LO Alkali metal perborate bleachillg agent. 5-15
Bleach activator ~TAED). 2.0-6.0
Sequestering agent for bleach. 0-3.0
Duet 787. 0-3.0
Optical brightener . 0 ,15-0.75
~ 15 Enz~rmes . 0. 75-1.25
;~ Perfume. 0 to 3.0
~ .
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The present invention is furth~r illustrated by the fc-lIo~-ing examples.
EXAMPLE 1
A high foam concentrated nonaqueous liquid nonionic surfactant
detel~cnt composition is forn~ulated from the follo~ing ingredients in the
amounts speci~ied.
Weight.Q6
9 li alkYl (CH2CH20)50H (I)
Sodium tri polyphosphate (TPP). 30.0
Diethylene glycol monobutylether anti-gel agent.( )13 7
Phosphoric acid alkanol ester (Empephos 5632). 0.3
Sodium perborate monohydrate ~leaching agent. 9.0
Tetraacetylethylene diamine (TAED) bleach activator. 4 . 5
A~lti-redeposition agent (Relatin ~M 4050) . (3) 1. 0
Optical bri~htener . 0 . 2
Perfume. 0. 6
Enzyme (which is Esperase). I.0
100.0
(1) The nonionic surfactant is available from Shell Chemical Co. under
the trademark Dobanol 91-5.
~ (2~ The anti-gel agent is available from Dow Chemical Ço. under the
trademark Do~anol DB
(3) CI~IC/I~C 2:1 mixture of sodium carboxymethyl cellulose and
hydroxymethylcellulose.
The formulation is ground for about I 0~ hour to reduce the particle size
of the suspended builder salts to ~ less than 40 microns. The formulated
dctergent com~osition is found to be stable and non-gelling in storage and
readily dispersible in water and to form a high stable foam in an aqueous
~- ash .
:
24
~3~66~ .
E X A.~IPLE 2
A high foam concentrated nonaqueous liquid nonionic surfactant
detergent composition is formuIated from the following ingredients in the
aoounts specified.
Weight .
Cg-Cll alkyl (CH2CH2O)5OH, (1) 36.7
; 5 Sodium tri polyphosphate (TPP). 34.0
Do~anol PIB-T anti-gel agent. ( ) 12 7
Phosphoric Acid Alkanol Ester (Empiphos 5632), 0 . 3
Sodium perborate monohydrate bleaching agent. 9.
Tetraacetylethylene diamine (TAED) bleach activator. ~ 4 . 5
Anti-redeposition agent (Relatin DM 4050).(3) 1.0
Optical brightener. 0 . 2
Perfume. 0 . 6
Ænzyme (~vhich is ~;sperase). 1.0
100.0
(1) The nonionic surfactant is available from Shell Chemical Co. under
the trademark Dobanol 91-5.
(2) The anti-gel agent is a mixture of mono-, di- and tripropylene
glycol~ monomethyl ether and is available from Dow Chem;cal Co.
; (3) C;~C/MC 2:1 mixture of sodium carboxymethyl cellulose and
~hydrosymethylceIlulose.
20 ~ ~ The formulation is ground ~or about 1.0 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
rcadily dispersible in water and to ~form a high stable foam in an aqueous
wash.
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1l ~3~
E~A!~1PLE 3
A high foam concentrated nonaqueous liquid nonionic surfactant
detergent composition u as formulated from the follo~ving ingredients in the
amounts specified.
¦ IYeight . 96
l Cg Cl1 alkyl (cH2cH2o)5oH (1) 36.4
¦ Sodium tri-polyphosphate (TPP Thermos NW). 29,6
Anti-incrustation agent (Sokalan CP5). 4.0
Diethylene glycoI monobutylether anti-gel agent.( ) 12.1
; Phosphoric Acid Alkanol Ester (Empiphos 5632),0.3
Sodium perborate monohydrate bleaching agent.9.0
Tetraacetylethylene diamine (TAED) bleaching agent. 4.5
Sequestering agent for bleach (Dequest 2066).1.0
Anti-redeposition agent (Relatin DM 4050~ . (3) 1.0
Optical brighteners (Stilben 4). 0.5
Enzyme (Esperase 8.0 slurry). 1.0
Duet 787. (4) 0.6
: 100.0
( 1 ) The nonionic surfactant is available from Shell Chemical Company
under the trademark Dobanol 91-5.
(2) The anti-gel agent ~is availab1e from Dow Chemical Company under
the trademark Dowanol D~.` ;
~ (3) CMG/MC 2:1 mixture of sodium carboxymethyl cellulose and _
. ~ hydroxymethylcellulose .
(4) Duet 787 is a fragrance an;d~ is a~ail~ble ~rom IFF, Inc.
The yield stress of the composition is 9 Pa, the plastic nscosity is
:: ~ : :
- ~ ~ 0.135 Pa. s at 25C snd the composition does not gel on dilution in water at
2~5 5C.
: ~ :
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.. i
The formulation is ground for about 1 hour to re~3uce 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
readily clispcrsible in water and to form a high stable foam in an aqueous
~Yash. During a miniwascator at a temperature of up to 60C washing cycle
the foam raised up to the dispenser, even in the presence of soil.
The formulations of Examples 1, 2 and 3 can be prepared without
grinding the builder salts and suspended solid particles to a small particle
size, but best results are obtained by grinding the formulation to reduce the
particle size of 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 mixing
them ~ith 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. The
formulations containing suspended builder and solid particles less than 40
microns in size are preferred.
It is understood that the foregoing detailed description is given merely
by t-ay of illustration and that ~rariations may be made therein without
departillg from the spirit of the invention.
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