Note: Descriptions are shown in the official language in which they were submitted.
7 !~ ~7 ~, 7 ~
6~3~ 450
HUILT NONA2UF,OUS l,IQUID NONIONIC LAUNDP~Y DETER~ENT COMPOSITIO~I
CONTAINING HEXYL~NE GLYCOL AND _ETHOD OF USE
~ACK~;ROUND OF THE INVENTION
., _ _
(1) Field of Inv~n~ion
This invention relates to nonaqueous liquid fabric
treating compositions. More particularly, this 1nvention
relates to nonaqueous liquid laundry de~ergen~ compositions
which are stable ayainst gelation~ are easily dispersible and
are ea.sily pourable and to the use of these compositions for
cleaning solled fabrics.
(2) Discussion of Prior Art
Liquid nonaqueous heavy duty laundry detergen~
compositions are well known in the art. For instance,
compositions of that type may comprise a liquid nonionic
surfactant in which are dispersed particles of a builder, as
shown for instance in ~he U.S.P. Nos. 4,316,812, 3,630,929 and
4,2~4,~66 and British Patent Nos. 1,205,711, 1,270,040 and
1,600,981.
The related Canadian applications assigned to the
common assignee are:
497,349 filed December 11, 1985 describes a
concentrated stable nona~ueous fabric ~oftener composition
comprising hexylene glycol alone or in combination with a lower
alkanol or another glycol or glycol ether, or mixtures thereof
as a liquid carrier for cationic fabric softeners, especially
the quaternary ammonium and imidazolinium cationic softeners.
The concentrated compositions may contain up to 60% by weight
of the cationic compound and may additionally include up to 15%
by weight of a nonionic surfactant.
1 7 r) 7 ~ ~ A~ 62 ~0 ~ 50
~9~, ai].5 f iled ~ecember 31, 1~6 describes a
nonacjueous 11~luid nonionic sur:factarlt detergent compositior,
comprisiny a suspension of a builder salt and containing an
acid term:ina1;ed noniorlic surrac-tant ( e . CJ ., the reaction prsduct
of a nonionic sur~actant anc~ suscinic anhydride) to impro~e
dispersibili~y of the composi~,ion in an au~omatic washing
machine.
1 / ~ 7 ~
62~01-l45
~ 9~1,8l5 flled Dec~mher 31, 1985 describes a
nonaqueous :Liquicl norllonic surfactant de~ergent composition
~omprising a ~usp~n~:Lon of bui Lc~er salt and ~ontainin~ aQ
alkylene qlycol mono-alkyl ether as a viscosi-ty and yel control
agent to improv~ dispersibility of the compositlon i~ an
automatic washin~ machine.
478,380 filed April 4, 19~5 describes a nonaqueous
liquid nonionic surfactant de-tergent composition comprising a
suspension of polyphosphate builder salt and containing an
alkanol ester of phosphoric acid to improve stability of the
suspension against settling in storaye.
Liquid detergents are often considered to be more
convenient to employ than dry powdered or particulate products
and, therefore, have found substantial favour with consumers.
They are r~adily measurable, speedily dissolved in the wash
water, capable of being easily applied in concentrated
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
incorporated in their formulations materials which could not
stand drying operations without deteriorationr 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 tOOr which
have to be overcome to produce acceptable commercial detergent
products. Thus, some such products separate out on storaye and
others separate out on cooling and are not readily redispersed.
In some cases the product viscosity changes and i~ becomes
either too thick to pour or so thin as to appear watery. Some
clear products become cloudy and others gel on standing.
l 7,!~7~3~
6~301-1450
The present inventors have heen lnvolved in studyi~g
the beha~iour of nonior~ liquid surl.-actant systems ~7i~h
parti~ulate matter suspended therein. Of parti~ular interest
has heen non~queous bu.ill; laundry liquid detergent compositions
and the problem ~f settling of the suspended builder and other
3a
lrlundry n(l(litives as ~cll ~s the problem of gelling s6sociated with nonionicsurfactants, Thcse considerations haYe fln impact on, for e~cample, product
stability, pourabi]ity and dispersibi~ity.
Jt is known that one of the major problcms with buill liqui(l laundry
S detergents is their physica~ slability. This problem stems from the f~ct that
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 ~end to settle out. Two basic
solutions e~cist to solve the settling out problem increase nonionic liquid
viscosity and reduce the dispersed solid particle size.
It is known that suspensions can be stabilized ~gainst settling by
adding inorganic or organic thickening agentg or dispersants, such as, for
example, very high surface area inorganic materials, e. g. finely div~ded
silica, clays, etc., organic thickeners, such as the cellulQse ethers, acrylic
and acrylamide polymers, polyelectroly~es, etc. However, such increases in
suspension viscosity are naturally limited by the requirement that the liquid
suspension be readily pourable and flowable, even at low temperature.
Furthermore, these additives do not contribute to the cleaning perfGrmance
of the formulation.
Grinding to reduce the particle size provides the ~ollowing advantsges:
1. Specirlc 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 bet~veen dispersed particles i~ reduced with ~
proportionate increase in particle-to-particle inter~ction. Each of these
cffects contributes to increase the rest-gel strength and the suspension yield
stress while at the same time, gr.nding significantly reduces plastic
viscosity.
The yicld strcss is defincd as the n)inimum strcss ncccssnry to induce a
plastic dc~rll~ation (flow) of tlle suspcnsion. Thus, visuali~ing the
~ 1 7rl7~7,A
suspension as a loosc nct~vork of dispersed partic1cs, if the app]ied strcss is
lower than the yield stress, the suspensi~n behaves lik~ an elastic gel and
no plastic flow will occur. Once the yield stress is overcome, th~ network
, breaks at some poinls and the samplle begins to flow, but with a very high
appar~nt viscosity. II the shear stress is much higher than the yie]d
stress, the pigments are partially shear-deflocsulated and ~he 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
present .
Therefore, the higher the yield stress of the suspension, the higher
the apparent viscosity at low shear rate and the better i8 the physical
stability against settling of the product.
IJI addition to the problem of settling or phase separation, the
nonaqueous liquid laundry detergents based on liquid nonionic surfactants
suffer from the dra~lback that the nonionics tend to gel when sdded to cold
water. This is a particularly important problem in the ordinary use of
European household automatic washing machines where the user places the
laundry detergent composition in a dispensing unit (e. g. a dispensing
drawer) of the machine. During the operation of the machine the detergent
in the dispcnser is subjected to a stream of cold water to transfer it to the
main body of wash solution. Especially ~uring the winter mor~ths when the
detergent composition and water fed to the dispenser are particularly cold,
the detergent ~iscosity 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 of the composition bllilsis up with
repeated wash cycles, eventually requirillg the user to flush the dispenser
with hot water.
The gclling phenvmenon can also be a prob~em whenever it is desired to
carry out W~S~ g U~Sing cold water as ~ay be recommended ~or certuin
S .~
~ 7~lt~
synthetic arlcl d~licate f~brics or fablics which can shrink in warm or hot
wuter .
The tend~ncy of concentrated detergent compositions to gel during
storage is aggrevated by storing the compositions in unhealed storage areas,
o~ by shipping th~ composilions during winter months in unheated
transportation vehicles.
Suspensions of bui2der salts, for example, sodium tripolyphosphates, in
nonaqueous liquid nonionic surfactant laundry detergent compositions are
characterized b~ a plastic viscosity and a yield stress value and an apparent
viscosity. The compositions which exhibit ~ high pl~stic viscosity also
exhibit a high yield stress value and are physically stable. However, in
compositions which have a high plastic viscosity, it is found that gel
formation is enhanced when the compositions are added to water. Normally
reducing the plastic viscosity dramatically reduces the yield stress value and
substantially reduces the physical stability of the composition. Further, for
the composition ~o be physically stable the apparent viscosity must be high.
However, high apparent viscosity usually adversely affects the dispersibility
of the composition in cold water.
Partial solutions to the gelling problem in aqueous, substantially builder
free compositions have been proposed, for example, by diluting the liquid
nonionic with certain viscosity controlling solvents and gel-inhibiting agents,
such as lower alkanols, e g4 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. In addition, tilese two pa~ents each disclose the use of up to
at most about 2 . 5% of the lower alkyl (C1-C4~ etheric derivatives of the
]ower ( C2-C3 ) polyols, e . g . ethylene glycol, in these aqueous liquid
builder-free dctergents in p]ace of a l>ortion of the lower alkanol, e. g.,
ethanol, as a viscosity COlltl'OI solvent . To simi]ar cffect are U . S ~ Patents
4,111,855 and 4,201,G86. Ilowever, thcre is no disclos,ure or suggestion in
~ 7 ~ ~ !
any of these p~ltcllts that these compounds, sorr3e of which ~re ~ommcrcially
svailable under the tr~c~ename Cellosolve (Registered Trademark), co-uld
function effectively as viscosity control ~nd gel-preventing ~gent~ for
, nonaqueous liquid nonionic surfactant compositions, especia]ly such
compositions cont~ining suspended b~,lilder salts, such AS the polyphosphate
compounds, ~nd especially particularly such compositions which do not
depend on or require the lower alkanol solvents as viscosity control ~gents.
As an example of nonionic surfactant modification for gel inhibition one
particularly successful result has been achieved by acidifying the hydroxyl
moiety end ~roup of the nonionic molecule. The advantages of introducing Q
carboxylic acid at the end of the nonionic include gel inhibition upon
dilution; decreasing the nonionic pour point; and formation of an anionic
surfactant when neutralized in the washing liquor. Nonionic structure
optimization has centered on the chain length of the hydrophobic-lipophilic
moiety and the number and make-up of alkylene oxide (e. g. ethylene oxide)
units of the hydrophilic moiety. For example, it has been found that a C13
fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a
limited tendency to gel formation.
Nevertheless, imprcvements are desired in both the ~tability, gel
inhibition and dispersibility of nonaqueous liquid fabric treating
compositions .
BRIEF DESCRIPTION OF THE INVENTION
In accordance with the present invention a highly concentrzted stable
nonaqueous liquid laundry detergerit composition is prepared by adding to
the composition hexylene glycol or hexylene glycol and propylene carbonate.
The compositions of the present invention contain hexylene glycol or
hexylene glycol and propylene carbonate.
The anti ~el and dispersil~ility properties of a llonaqueous liquid
llOlliOlliC surfactant laundry detergent composition nre improved by the
~llddilion of hexylene glycol to the composition. The a~ldition of h~sylelle
I ~ 1 ~'J743~
glycol l'CdUCCS Ihe plnstic viscosity of ti)e com~osi~ion ~vith little or no
advcrsc affcct on yield strcss ~alue of the composition~or adverse af~ect on
the physical stability of t~le composition. The addition of hexylene glycol
and propy]cne carbonate to the no~ionic surfactant composition substantially
reduces the ~pparcnt viscosity of the composition and ~ubstantially improves
the dispersibilily of the composition.
The hexy]ene glycol and propylene carbonate ~hen added tc~ the
compcsition improve the disper sibility of the suspension of builder salt by
acting to inhibit gel formation of the suspension of builder sai~. The
hexylene glycol and propylene carbonate improve dispersibility by inhibiting
gel formation of the suspension of detergent builder salt p~rticles when
t~ater is added to the composition, for example, in the dispensing drawer of
a washing machine and/or when the composition is added to water.
In order to improve the viscosity characteristics of the composition an
acid terminated nonionic surfactant can be added. To improve the storage
properties of the composition there can be added to the composition an anti
settling agent such as phosphoric acid ester.
Sanitizing or bleaching agents and activators therefor can be added to
improve the bleaching and cleansing characteristics of the compositlon.
In an embodiment of the invention the builder components of the
composition are ground to a particle size of less than 10û microns, e. g. ]ess
than ~0 microns and preferably less than lO microns to further improve the
stability of the suspension of the builder components in the liquid nonionic
surfactant detergent.
In addition other ingredients can be added to the composition such as
anti~ crustation agents, anti-foam ngents, optical brighteners, enzymes,
anti-redcpositioll agellts, perfume and dyes.
~2:~0~.-14sr
The pre~ntly ~l~nufacture~i~h~ ~ machine~ for home
use norma:lly operate at; ~ashiny temperatllres of up to ~0 C.
About 18.5 yallons (70 liters) of water are used dl1ring the
wash and rinse cy-les.
About Z00 to ~50 gms of powder detergent per wash iB
normally used.
In accordance with the present invention where the
concentrated li~uid detergent is used normally only lO0 gms
~78 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 detergent composition which comprises at least one
liquid nonionic surfactant in an amount from about 10 to about
80 percent by weight, at least one detergent builder salt
suspended in the nonionic surfactant in the amount of about 10
to about 60 percent by weight, hexylene glycol in the amount of
about 5 to about 40 percen~ by weight and up to about 5 percent
hy weight of a carbonate of the formula
o
C
O O
R - CH - CH - R
wherein R1 and R2 are members selected from the group
consisting of H and C1 to C4 lower alkyl and R1 and R~ are ~he
same or different.
According to another aspect, the invention provides a
concentrated liquld heavy duty laundry detergent composition
which is stable, non-settling in storage and non-gelling in
storage and in use. The liquid compositions of ~he present
invention are easily pourable, easily measured and easily put
into the washing machine and are readily dispersi~le in wat.er.
I n ,7 ~ 3 ~ G;J~r~
~ 'eO~d:i(lCI to arlOtllC`r :ISi')fCt,, tl~e i,llVenl,:iOn p~`OVl'le'-' a
methocl for disperls,ng ., ~ d rlonionic :!-)urldry detercJerlt
~oil~pc.~ition i~ito a~d/oL ~.~ith ~ d w~ter without und~rgoincJ
gelatioll. In part~ , a methc,d is provided for fil]iny a
container wit.h a nonacluf-~ous liquid laundr-~ cleteryent
composition in ~Jhich the deteryent is ~omposec', a-t ].east
predomirlantly, o-f rl liquid nonionic surface ae~ive ~gent and
for dispensing the eompos,ition from the con-tainer into an
aqueous ~rash bath, wherein the dispensing i.Y effected hy
directing a stre;am of unheated water onto the composition such
that the composition is carried by the stream of wa-ter into the
wash ha-th.
ADVANTAGES OV~R THE PRIOR ART
The adclition of hexylene glyeol to the eomposi-tion
substantially reduees the plastie viseosity nf the eomposition
with little or no reduetion in the yield stress value and
little or no reduetion in the physieal stability of the
eomposition. ~he addition of hexylene glyeol and propylene
earbonate to the eompositi.on s!~bstantially reduees the apparen~
viseosity of the eomposition and substantially improves the
clispersibility. The addition of hexylene ylyeol or hexylene
ylyeol and propylene earbonate to the eomposition prevent the
gel formation usually oeeurring when the eomposition is
eontaeted wi.th eolcl water and aeeordingly improves
dispersihility.
The coneentrated nonagueous li~uid nonionie
surfaetant laundry detergent eompositions of the pre.sent
invention have the advantayes of beiny stable, non-settliny in
storage, and non-yelling in storage. The liquid eompositions
3~ are easily pourable, easily measured and easily put into the
iaundry washing machine~ and are readily dispersible in water.
~0
, ~J
7 ~
6~3~ 5
A IS _F T~lh_INVENTLON
The present :irlvention seeks to prov:ide a stable
liquid heavy duty nona~ueou.s nonionic de~ergent composi~ion
containing he~ylene yly~ol OI hexylene glycol and propylene
carbonate and an anionic phospha~e detergent builder salt
suspended in a nonionic surfactant.
The lnvention also seeks to provide liquid fabric
treating compositions which are suspensions of insoluble
inorganic particles in a nonaqueous liquid and which are
storage stahle, easily pourable and dispersible in cold, warm
or hot wateL.
This invention also seeks to formulate highly built
heavy duty nonaqueous liquid nonionic surfactant laundry
detergent compositions which can be poured at all te~peratures
and which can be repeatedly dispersed from the dispensing unit
of European style automatic laundry washing machines without
fou].ing or plugging of the dispenser even during the winter
months.
This invention further seeks to provide non--gelling,
stable suspensions of heavy duty built nonaqueous liquid
nonionlc laundry detergent compositions whlch include an
effective amount of hexylene glycol to substantially reduce the
plastlc viscosity with little or no ~educti~n in yield stress
value of the compositions.
This inventlon also seeks ~o provide a non-gelling
readily dispersihle, stable suspensions of heavy duty built
nonaqueous liquid nonionic laundry detergent compositions which
include an effective amount of hexylene glycol and propylene
carbonate to substantially reduce the apparent vi~cosity and to
substan~ially improve the dispersibility of the composition.
~ 11
', 7 r! 7 ~
T~ lVf`ni~ n ~J:i. l! b~-~o(ne more ap~-lxel-lt frc,rn ~tle
~oliowil-lg detd~led descli.ption of- pre~:erred embodimerlts r,7h.-je~}l
ar(-. cJenerally provided io~ hy preparlng a de-tergenl ~o~poslt.ion
by addi.ncl to the r,orlaclueolls 1~ ui~ noni.orlic surf-letant an
effective amoul~t ol lleXyle!~ gly~ol o~ hexylene glycol and
propylene carbonate sufflcierlt to inl1ibit gelling of -.:he
eompositiol-l, whiie maintalning physical stability of the
composition, wherein said composit;Lon ineludes inorgarlic or
organic fahric treating additives, e.y. viseosl-ty improving
agents ancl one or more anti--gel agents, anti-i.ncrustation
agerJts, pH con-trol agents, bleaehing agents, bleaeh activators,
anti--foam agents, optieal brighteners, en~ymes, anti-
recleposition agents, perfume, dyes ancl coloring pigments.
DETAILED_DESCRIPTION OF THE INV NTION
In ac~ordanee with the present invention the anti-gel
properties and the dispersibility properties of the nonaqueous
liquid nonionie surfac~tant laundry composition are
substantially improved by thè addition to the composition of
hexylene glyeol or hexylene g].yeol and propylene earbonate.
The hexylene gly~ol or hexylene glycol and propylene
earbonate when added to the eomposition improves the
~ispersibility of the suspension of builcler salt by acting to
inhibit gel formation of the suspension of builder when
eontactecl. with water.
The hexylene glyeol or hexylene glyeol ancl propylene
carbonate improves cdispersibility by inhibitin~ gel formation
of the suspension of detergent builder salt partieles when
water is added to the co~position, for
~ llc~
~ l ~
1 7n743/!
example, in the dispensing drawer of a washing maclline andtor when the
composition is added to the wash ~ater.
The anti-gel and dispersibility properties of a nonaqueous liquid
l ~ nonionic surfactant laundry detergent composition are improved by the
5addi~ion of hexylene glycol to the composition. The addition of hexylene
glycol reduces the p~astic viscosity of the composi~ion with little or no
adverse affect on yield stress value of the composition and with little or no
adverse affect on ihe physical stability of the composition. The ~ddition of
hexylene glycol and propylene carbonate to the nonionic surfactant
10composition substantially reduces the apparent viscosity of the composition
and substantially improves the dispersibility of the composition.
The hexylene glycol can be used alone or in admixture with Cl-C3
~kanol, for example ethanol or propanol, a C2-C4 glycol, preferably
diethylene glycol or propylene glycol, or a C1-C" mono- or di-alkyl ether of
15such glycols or mixtures thereof. Hexylene glycol in its commercially
¦ available form is comprised primarily of 2-methyl- pentane-2, 4-diol. The
¦ term hexylene glycol is intended to include 2-methyl-pentane-2, 4-diol as
well as other isomeric diols with the generic formula C6Hl;~(OH)~, e. g.
hexane-1, 3-diol, hexane-1, 4-diol, etc.
20The propylene carbonate used in accordance with the present invention
has the formula O
/c\
C H - - C l l - C H
The lower alkyl carbonates having the formula
li .
Rl--- CH-- CH R~2
.
12
7~r) 7~ 7)~' I
~vhcl~ein Rl and R2 are H~ Cl~3-, C2H5-~ and C4Hg-, and R1 and R2 can be
the same or diff~rent can also be used in accordance with the present
invention .
The pr/~pylene carbonate when added to the compositiOn, even in small
amounts, increaSeS the polarity of the matrix and helps the dispersibility in
water. The propylene carbonate is also a gel control agent. The propylene
cal bonate is essential in the presence of Bentones ~or which it acts as 8
polarity booster to help their swelling. The recommended le~el of propylene
carbonate is about one third that of the Bentone on a weight basis, e.g.
about 0.5 gm propylene carbonate to about 1.5 gm of Bentone.
Nonionic Surfactant Detergent
The nonionic synthetic organic detergents employed in the practice of
the invcntion 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 attached to
the nitrogen can be condensed with ethylene oxide or with the polyhydration
product thereof, polyethylene glycol, to form a non;onic 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 4,316,812 and 3,630,929.
Usually, the nonionic detergents are poly-lower alkoxylated lipophiles
whcrcin the desired hydrophile-lipophile balance iS obtaincd from addition of
a hydrop]~ilic poly-lower alkoxy group to a lipophilic moiety. A preferred
class of the nol~ionic deterg~cllt cnlploycd iS the poly-lower alkoxylated higher
alkanol wherein the a]kanol is of 9 to 18 carbon atoms and whereill the
~1 13
l ~ 17.,rl7~3~
number of mols of Ic>wer alkylene oxide (of 2 or 3 carbon lltoms) is from 3 to
12, Of such materials it is prefel red to e~ploy those wherein the higher
alkanol is a higl~er ffltty nlcohol of 9 to 11 or 12 fo 15 carbon atoms and
, which cont~in from 5 to 8 or 5 t~ 9 10~er alkoxy groups per mol.
Preferably, the ]ower alkoxy is ethoxy hut in some inStanCeS, it may be
d~sirably mixed with propoxy, the lat~er, if present, often being a minor
(less than 50~) proportion.
Excmplary 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 N7eodol 23-6, 5, which products are made by Shell
Chemical Company, ~nc. The former is a condensation product of a mixture
of higher fatty alcohols averaging about 1~ to 15 carbon atoms, with about 7
rnols of etllylene oxide and the latter is a corresponding mixture wherein the
carbon atom content of the higher fatty alcohol is 12 to 13 and the rlumber
of ethylene oxide groups present averages about 6.5. The higher alcohols
are primary alkanols.
Other examples of such detergents include Tergitol~5-S-7 and Tergitol
15-S-9, both of which are linear secondary alcohol ethoxylates rnade 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 is a similar product but with nine mols of ethylene oxide being
reacted .
Also useful in the present composition as a component of the nonionic
dctergent are higher molecular weight nonionics, such 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 nl~mber of et11ylclle oxide groups per mol being about 11. Such product~
are also made by Sllell Chcmical Company.
Other useful nonionics are re~resented by the commercially well known
class of nonionics sold ullder the tradcmtlrlc Plurafac, The Plurafacs are the
~ l^f;! ~ D ~ C ~
1~ ~
1 7 !~ 7 ~t 3 ~ ~ - -
re~lction product of ~ }lig~ler linear alcohol and a mixture of ethylcne and
propylene oxides, containing a mixe~ chain of ethylene oxide and propylene
oxide, termin~ted by a hydroxyl gro~lp. Examp]es include products which
are (A) C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3
moles propylene oxide, (B) C13-C15 fatty a3cohol condensed with 7 moles
propylene oxide and 4 moles ethylene oxide9 (C) C13-Cl5 fatty alcohol
condensed with 5 moles propylene oxide and 10 moles ethylene oxide, and
(D) which is a 1:1 mixture of products (B) and (C).
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 Doballol 25-7 is an ethoxylated C12-Cl_ fatty alcohol with an average of
7 moles ethylene oxide per mole of fatty alcohol.
In the preferred poly-lower alkoxylated higher alkanols, to obtain the
best balance of hydrophilic and 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
2 0 solid nonionic detergents and surface active agents may be contributory togelation of the liquid detergent and consequently, will preferably be omitted
or limited in quantity in the present compositions, slthough 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
tolcrated, such as at a carbon next to or two carbons removed from the
ternlinal carbon of the stra~ight chain and away from the ethoxy chain, if
such branched alkyl is not more than thlee carbons in lcngth. Normally,
the proportion of carbon atoms in such a branclled configuration will be
minor r;lrcly cxcecdillg 20% of the total carl)on atom COIltCnt of the alkyl.
~ l ~ n 7 ~ 7,~
Similarly, althovg~ r .llkyls which are terminally joined to the ethylene
oxide chains are highly prcferred and are considered to resul~ in the best
combination of dctergency, biodegradability and non-ge11ing characteristic~.
medial or secondary joinder to the ethylene oxide in the chain m~y occur. It
5 ' is usually in ~>nly a minor l~roportion of such alkyls, generally less than 20%
but, as is in the cases of the mentioned ~rl~ols, may be greater. Also,
when propy3ene oxide is present in the lower alkylene oxide chain, it will
usually be less than 20~ thereof and preferably less than 10~ thereof.
When gr~ater proportions of non-terminally alkoxylated alkanols,
propylene oxide-containing poly-lower alkoxylated alkanol~ and less
hydrophile-lipophile balanced nonionic detergent than mentioned above are
employed and ~hen other nonionic detergents are used instead of the
preferred nonionics recited herein, the product resulting may not have as
good detergency, stability, viscosity and non-gelling properties as the
preferred compositions but use of the viscosity and gel sontrolling
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 its detergency,
the proportion thereof will be regulated or limite~ in accordance with the
results of routine experiments, to obtain the desired detergency and still
have the product non-gelling and of desired viscosity. Also, it has been
found that it is only rarely neccssary to u~ilize the higher molecular weight
nonionics for their detergent properties since the preferred nonionics
described herein are excellent detergents and sdditionally, permit the
attainment of the desired viscosity in the liquid detergent t~ithout gelntion at
low temperatures.
Another useful group of llonionic surfactallts are the "Surfactant T"
scries of nonionics a~ailabe from British Petroleum. The Surfactant T
nonionics are obtaincd by the ethoxylation of secolldary C13 fatty alcohols
llaving a nalrow othylcl-e oxide distril>ution. Tl~e Sul;factant TS l as an
3~ 13 ~ IhAA~ 16
1 7~n7434 62301-1450
average of 5 moles of ethylene oxide; Surfactant T7 an avexage
of 7 moles of ethylene oxide; Surfactant T9 an average of 9
moles of ethylene oxide and Surfactant Tl2 an average of 12
moles of ethylene oxide per mole of se~ondary C13 fatty
alcohol.
In the compositions of this inventlon, preferred
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 with about 5-6 mole~ e~hylene oxlde.
Mixtures of two or more of the liguid nonionic
surfactants can be used and in some cases advantages can be
obtained by the use of such mixtures.
Acid Terminated Nonionic Surfac~ant
The ~iscosity and gel properties of the liquid
detergent compositions can be improved by including in the
compositlon an effective amount of an acid terminated liquid
nonionic surfactant. The acid terminated nonionic surfactants
consist of a nonionic surfactant which has been modified to
convert a free hydroxyl group thereof to a moiety having a free
carboxyl group, such as an ester or a partial ester of a
nonionic surfactant and a polycarboxylic acid or anhydride.
As disclosed in the commonly assigned Canadian
application No. 478,379 filed April 4, 1985, the free carboxyl
group modified nonionic surfactants, which may be broadly
characterized as polyether carboxylic acids, function to lower
the temperature at which the liquid nonionic forms a gel with
water.
The addition of the acid terminated nonionic
surfactants to the liquid nonionic surfactant aids $n the
dispensability of the composition, i.e. pourability, and lowers
, ~ ~ 7 ~ ) ? 6~30~ 50
the ~emperature at which -the 11quid nonionic surfactants form a
gel in wa~er wi~hout a decrease in ~ he:ir s-tabi.1ity against
settl.ing. The acid ter.ninatecl nonionic surfactant reacts in
the washing machirle water with the a1ka1inity of the dispersed
builder sa] t ph?lse o:~ the deterg~nt composition and acts as an
effective anionic surfactant.
17a
~ l7, n~ 7)~
Specific ~xamplcs i~clude the hnlf-esters of product (A) with succinic
anhydride, the ester or half cster of Dobanol 25-7 with succinic anhydride,
and the ester or half cster of Dobanol 91-5 with succinic anhydride. Instead
of succinic anhyflride, other polycarboxylic acids or anhydridcs can be used "
S e. g. maleic acid, maleic acid anhydride, glutnric acid, malonic acid, phthalis7
acid, phthalic anhydride, citric acid and the like.
The acid terminated nonionic surfactants can be prepared as follows:
Acid Terminated product (A). 400g 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 units per alkanol unit is mixed with
32g of succinic anhydride and heated for 7 hours at 100C. The mixture is
cooled and filtered to remove unreacted succinic material. Infrared anslysis
indicated tha~ about one half of the nonionic surfactant has been convertcd
to the acidic half-ester thereof.
Acid Terminated Dobanol 25-7. 522g of I)obanol 25-7 nonionic
surfactant which is the product of ethoxylation of a C12 to C15 alkanol and
has about 7 ethylene oxide units per molecule of alkanol is mixed with lOOg
of succinic anhydride and 0. lg of pyridine (which acts as an estelification
catalyst) and heated at 260C for 2 hours, cooled and filtered to remove
unreacted succinic materiale Infrared analysis indicates that substantially all
the free hydroxyls of the surfactant have reacted.
Acid Terminate Dobanol 91-5. 1000 of Dobanol 91-5 nonionic surfactant
~hich is the product of ethoxylation of a Cg to Cll alkanol and has about 5
ethy]ene oxide units per molecule of alkanol is mixed with 265g of succinic
anllydride and 0.1g of pyridine catalyst and heated at 260C for 2 hours,
cooled and filtered to remove unreacted succinic matcrial. Infrared analysis
inclicates that sul~stantially all the free hydroxyls of the surfactant have
reacted .
18
1 17'1743~
Other estel if ication catalysts, such a~ an a]ka~i met~ alkoxide (e. g.
sodium methoxide) may be used in place of, or in admixture with, the
pyridine .
The acidic polyct},er compoun~, i . e . the acid termingted noniollic
surfactant is preferably added dissolved in the nonionic surfactant.
BUILDER SALTS
The liquid nonaqueous nonionic surf~ctant used in the compositions of
the present invention has dispersed and suspended therein fine particles of
inorganic and/or inorganic detergent builder sslts.
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 admixture
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 Rnd diorthophosphate, and potassium bicarbonate. ~odium
tripolyphosphate (TPP) is especially preferred.
Since the compositions of this invention are generally highly
concentrated, and, therefore, may be used at relatively low dosages, it is
desirable to supplement any phosphate bui]der (such as sodium
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 otller~Yise be caused by formation of an
insoluble calcium phosphate.
A suitable lo~ver poly carboxylic acid compriscs alka~i metal salts of
lo~cr polycarboxylic flCiC~S, preferably the so(lium and potassium salts.
Suitable lo~vcr pol~c~rhoxylic acids have t~ o to four c~rboxylic acid groups.
. `
19
l 7,~ 7 ~ ) ~ 623~ 0
The preferred sodium and potassium lower polycarboxy].ic aids
salts are ~he citric and tartaric ac~id sa1ts.
The sodium citric acid .æa]ts are the most preferred,
especially the trisodiuM cit.ra~e. 17he monosodium and disodium
citrates can also be ~sed. The monosodium and disodium
tartaric acid salts can also be used. The alkali metal lower
polycarboxylic acid salts are particularly good builder salts;
be~ause of their high calc1um and magnesium binding capacity
they inhibit encrustation which could otherwise be caused by
formation of insoluble calcium and magnesium salts.
Other oryanic builders are polymers and copolymers of
polyacrylic acid and polymaleic anhYdride and the alkali metal
salts thereof. ~lore specifically such builder salts can
consist of a copolymer which is the reaction product of about
equal moles of methacryli~ acid and maleic anhydride which has
been completely neutrali~ed to form the sodium salt thereof.
The builder is commercially available under the trademark of
So,calan CP5. This builder serves when used even in small
amounts to inhibit encrustation.
Examples of organic alkaline sequestrant builder
salts which can be used with the detergent builder salts or in
admixture with other organic and inorganic builders are alkali
metal, ammonium or substituted ammonium, aminopolycarboxylates,
e.g. sodium and potassium ethylene diaminetetraace~tate (EDTA~,
sodium and potassium nitrilotriacetates (NTA), and
triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates. Mixed
salts of these aminopolycarboxylates are also suitable.
Other suitable builders of the organic type include
carboxymethylsuccinates, tartronates and glycollates. Of
special value are the polyacetal carboxylates. The polyacetal
carboxylates and their use in detergent compositions are
1 ~ ~ 7 4 3 ~! 62301-1450
described in Cana~;lian applicatiorl No. 51S,256 filed August 19,
ls86 ass:igned to ~pplicants' ~ssignee and in a U.S.P. Nos.
4,144,226, 4,315,0~ and 4,146,~95
The allcali metal sil:~cates are useful builder salts
which also func~ion to adjust or control the pH and -to make the
composition anticorroslve to washing machine parts. Sodium
silicates of Na20/SiO2 ratios of from 1.6/1 to 1/3~2,
especially about 1/2 to 1/2.8 are preferred. Po~assium
silicates of the same ratios can also be used.
Other typical suitable builders include, for example,
those disclosed in U.S. Patents 4,316,812, 4,264,46fi and
3,630,929. The inorganic builder salts can be used with the
nonionic surfactant detergent compound or ln admixture with
other inorganic builder salts or with organic builder salts.
The ~ater insoluble crystalline and amorphous
aluminosilicate zeolites can be used. The zeolites generally
have the formula
( 2o)x-(Al2o3)y-(si~2)z-wH2o
wherein x is ]., y is from 0.8 to 1.2 and preferably l, z is
from 1.5 to 3.5 or hlgher and preferably 2 to 3 and w is from O
to 9, preferably 2.5 to 6 and M is preferably sodium. A
typical zeolite is type A or similar structure, with type 4A
particularly preferred. The preferred aluminosilicates have
calcium 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 Bri~ish Patent 1,504,168,
U.S.P. 4,409,136 and Canadian Patents 1,072,835 and 1,087,477.
An example of amorphous æeolites useful herein can be found in
Belgium Patent ~35,351.
1 3()743~
623~1-1450
Other m~terials su~h as clays, particularly of the
water-insoluble types, may be useful adjuncts in compositions
of ~his invent.ion. Particularly useful is bentonite. Thls
material is primarily montmorillonite which i5 a hydrated
aluminum ~il1eate in which about 1/~th of the aluminum atoms
may be replaced by magne~ium atoms and Wi~h Whi.ch varying
amounts of hydrogen, sodium, potassium, calcium, etc., may be
loosely combined. The bentonite in its more purified form
(i.e. free from any yrit, sand, etc.) suitable for detergents
lo contains at least 50% montmorillonite and thus its cation
exchan~e capaci~y iS at least about 50 to 75 meq per 100 g of
bentonite. Particularly prefe~red bentonites are the Wyoming
or Western U.S. bentonites which have been sold as Thixo-jels*
1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known
to soften textiles as described in British Patent 401,413 to
Marriott and British Patent 461,221 to Marriott and Guan.
There can also be added to the compositions of the
present invention small amounts of Bentones, e.g. of Bentone-27
which ls an organic derivatlve of magnesium aluminum silicate
and which in the composltion functions as an anti-settling
agent.
The Bentones, e.g. Bentone-27 can be added in amounts
o~ 0.05 to 3, such as 0.2 to 2, e.g. about 0.5 to 1.5%.
The compositions of the present invention have
improved viscosity and stability characteristics and remain
stable and pourable at temperatures as low as about 5C and
lower.
The hexylene glycol or hexylene glycol and propylene
carbonate act to improve the dispersibility of the suspension
of phosphate detergent builder particles by inhibi~ing gel
formation of the suspended particles when cold water is added
*Trade-Mark 22
1 ir,74 A
6~ 50
to the CO~pO~itiOIl in the dispensin~ dra~Jer and/or when the
composition is added -to ~ater.
In an em~-Jodiment of thi, invention a stahilizing
agent which is an alkanol ~ster of phosphoric acid can be added
to the formulation. Improvements in stablllty of the
composition may be achieved by incorporatlon of a small
effective amount of an acidic organic phosphorus compound
having an acidic - POH group, such as a partial ester of
phosphorous acid and an alkanol.
As disclosed in the commonly assiyned Canadian
application No. 478,379 filed April 4, 1985, the acidic oryanic
phosphorous ~ompound having an acidic - POH
22a
~ 1 7 r~ 7 ~
group can increase the stability of ~he suspension of ~uilders in the
nonaqueous ]iquid nonionic sur~ctant.
The acidic organic phosphorus compound rnay be, for insfance, a partial
; ester of phosphoric DCid and an alc:oho~ such as an alkanol which has a
lipophilic character, hav;ng, for instarlce, more lhan 5 c~rbon atoms, e.g. 8
to 20 carbon ~toms.
A specific example is a partial ester of phosphoric acid and a C16 to
i C18 ~Ikanol (Empiphos 5632 from Marchon); it is made up of about 35%
monoester and 65% diester.
The inclusion of quite small amounts of the acidic organic phosphorus
compound makes the suspension stuble against settling on standing but
remains pourable~
Another additive compound that can be added to the composition is
Arosurf TA 100 which is distearyl dimethyl ammonium chloride. The Arosurf
TA 100 functions in the composition as a rhcology additive to improve the
product physical stability. The Arosurf TA 100 can be added in amounts of
0. 05 to 4, such as 0.5 to 1.5, e.g. about 0.1 ~o 1.0%.
Bleaching Agents
The bleaching agents are classified broadly, for convenience, as
chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by
sodium hypochlorite (NaOCl~, potassium dichloroisocyanurate (59% available
chlorine), and trichloroisocyanuric acid (95% available chlorine). Oxygen
bleaches are preferred and are represented by pereompounds which liberate
hydrogen pcroxide in solution. Preferred examples include sodium and
potassium perborates, percarbonates, and perphosphates, and potassium
monopersulfate. The perborates, particularly sodium perborate monohydrate,
are cs~ccially prefcrred.
The pcloxygen compound is prcferably ~lsed in admixture with an
activator ti~el cfor. Suitnble activators can lower the effective operating
tempel,lt Ire of the pcioxide bleac}ling ngent. I?olyncylated compoullds are
4~
23
1 ~ ~ 7 4 3 ~ ~2301-1~50
preferre-l ac~ivators; amor.g these, compound.s such a.~
tetraacetyl e~.hylene diamine ("TAED") ~nd pentaacet-yl glucose
are par~icularly preferred.
Other useful activators in~ de, for example,
acetylsalicylic acid derivatives, ethylidene benzoate acetate
and its salts, athylidene carboxylate acetate and it5 salts,
alkyl and alkenyl succinic anhydride, tetraacetylglycouril
("TAGU"3, and the derivatives of these. Other useful classes
of activators are di.sclosed, for example, in U.S.P. 4,111,8~6,
~,422,950 and 3,661,789.
The bleach activator usually interacts with the
peroxygen compound to form a peroxyaci.d bleaching agen~ 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 ~his purpose inc:lude
the sodium salts of nitrilotriacetlc acid (NTA), ethylene
diamine tetraacetic acid (EDTA), diethylene triamine
pentaacetic acid (DETPA), dlethylene triamine pentamethylene
phosphonic acid (DTPMP) sold under the tradename Dequest 2066;
and ethylene diamine tetramethylene phosphonic acid (EDITEMPA).
The sequestering agents can be used alone or in admixture.
In order to avoid loss of peroxide bleaching agent,
e.g. sodium perborate, resulting from enzyme-induced
decomposition, such as by catalase enzyme, the compositions may
additionally include an enzyme inhibitor compound, i.e. a
compound capable of inhibiting enzyme-induced decomposition of
the peroxide bleaching agent. Suitable inhibitor compounds are
disclosed in U.S.P. 3,606,990.
24
~ 7,~7~ 7`,~
62~J1~1~5(~
Of spe~ia] interest as the inhibitor ~ompound,
mention ~an be m~lcle of hydLoxylamine ~uliate and other ~7ater-
.soluble hydroxylamlne ~al~. In the preferrer~ nona~ueous
oompositions of this in~ent:ion, sult,able amounts of the
hydroxylamine sal t i.nhihi-tors can h~ aS low as about 0.01 to
0.4%
24a
1 7~r~747~Ç~,
Ccncrally, however, suitable amo-lnts of enzyme inhibitors are up to about
15%, for example, 0 1 to 10%, by ~eight of the composition.
In addi~ion to ~he detergent builders, various other detergent addi~ive~
or adjuvants may be present in the detcrgen~ product to give it ndditional
desired properties, either of functional or aesthetic nature. Thus, there
may be included in the formulation, minor amounts of soil suspending or
an~i-rcdeposition agents, e.g. po~yvinyl alcohol, fatty amides, sodium
carboxymethyl cellulose, hydroxy-propyl methyl cellulose. A preferred
anti-redeposition agent is sodium carboxymethyl cellulose having a 2 :1 ratio
~ ~ ~ r a ~
of CMC/MC which is sold under the trn~a.m~ Relatin DM 4050. /
Optical bri ghteners for cotton, polyamide and polyester fabrics can be
used. ~uitable optical brighteners include stilbene, triazole and benzidine
sulfone compositions, especially sulfonated substituted triazinyl stilbene,
sulfonated naph~hotriazole stilbene, benzidene sulfone, etc., most preferred
l 5 are stilbene snd triazole combination~ .
Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin,
papain, trypsin and pepsin, as wel~ as amylase type anzymes ~ lipase type
enzymes, and mixtures thereof can be added. Preferred enzymes include
protease slurry, esperase slurry and amylase. A preferred en~yme is
Esperse~;L8 which is a proteolytic enzyme. Anti-foam agents, e.g. silicon
compound, such as Silicane~L 7604, ~lhich is polysiloxane can also be added
in small efrective amounts.
Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene,
fungicides, dyes, pigments (~vater dispersible), preservatives, ultraviolet
absorbers, ant;-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 nlso contain an inorganic insoluble thickening agent
or dispersant of vcry high surface area such as fil~ely divided silica of
cxtrcmcly fine particle si~e (e. g. of 5-100 millimicrolls ~linmcters such as sold
R ~1;~6 ~
~ t7r~17ll7,~
under the name Aerosil) or ~he other highly volumin~us inorganic carrier
materials disc]osed in IJ.S.P. 3,630,929, in proportions of 0.1-109~, e.g. 1 to
5%. It is preferable, however, tha~t 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 and silicates promote
the undesired decomposition oî the pcroxyacid.
In an embodiment of the invention the stability of the builder salts in
the composition during storage and the dispersibility of the s~omposition in
water is improved by grinding and reducing the particle size of the solid
builders to less than 100 microns, preferably less than 40 microns and more
preferably to less than lO microns. The solid builders, e.g. sodium
tripolyphosphate (TPP), are generally supplied in particle sizes of about
lO0, 200 or 400 microns. The nonionic liquid surfactant phase can be mixed
l~ith 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 about 10 microns, e.g. to an average particle size OI 2 to 10 microns or
even lower (e.g. 1 micron). Preferably less than about 10%, especially less
than about 5% 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
~lithout a corresponding decrease in the dispersions stubility against
settling .
In the ~rinding opcration, it is preferred that the proportion of solid
ingl~c(lients be hig11 cnough (e. g. at least about 40% such as about 50%) that
the solid }~;~1 liclcs are in colltact with cnch other alld are not substantially
. '
2C
~ 7~ n 7 ~
shielded from one anothcr by the nonionic surfflctant ]iquid. After the
grinding step any remaining liquid nonionic surfactant can be added to the
ground formulation. Mills which employ grinding ba~ls (ball mills) or similar
.mobile grinding elements have given ~ery good rcsults. Thus, one may use
a laboratory batch attritor hav~ng ~ mm diameter steatite grinding balls. F~r
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 gnp between 8 stator
and a rotor operating at a relatively high speed (e. g. a CoBsll mill) may be
employed; when using such a mill, it is desirable to pass the blend of
nonionic surîactant and solids first through a mill which does not effect such
~lne grinding (e.g. a colloid mill) to reduce the particle size to less than 10Cmicrons (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 80,
such as 20 to 70 percent, e.g. about 30 to 70 percent.
Detergent builder, such as sodium tripolyphosphate (TPP), in the rnnge
of about 10 to 60, such as 15 to 50 percent, e. g. about 20 to 35.
Hexylene glycol in an amount of about S to 40 percent, or 5 to 30
percent such as 10 to 30 percent, e. g. about 20 to 30 percent.
Propylene carbonate in an amount of about 0 tc- 5 percent, such as 0.1
to 1. 0 or 0 .1 to 2 . 0 percent, e . g. 0 . 2 to 0 . 8 percent .
Acid terminated nonionic surfactant in an amount in the range of about
0 to 20, such as 3 to 15 percent, e.g. about 4 to 10.
Alkali metal silicate in the rallge of about 0 to 30, such as 5 to 25
pcrcent, e. g. about 10 to 20.
. :
27
7 ~ 7 ~
l COpO]ymer of polyacrylate andl polymaleic anhydride alkali rretal sa]t,
¦ e.g. Sokalan CP5, anti-incrustation a~ent in the range of about 0 to 10,
¦ such as 2 to 8 percent, e.g. about 3 lo 5.
¦ Phosphoric acid alkanol ester stabi~i~ing agent in the range of 0 to 2 . 0¦ or 0 .1 to 2 . 0, ~uch as 0 .10 to 1. 0 percent .
B]eaching agent in the range of abou~ 0 to 30, such a~ 2 to 20, e.g.
about 5 to 15 percent.
Bleach activator in the range of about 0 to 15, such as 1 to 8, e.g.
l about 2 to 6 percent.
l Segaestering agent for bleach, e.g. Dequest 2066, in the rang~ of
about 0 to 3 . 0, preferably 0 . 5 to 2 . 0 percent, e . g. about 0 . 75 to 1. 25
percent .
Anti-redeposition agent, e.g. Relatin DM 4050, in the range of about 0
l to 4.0, preferably 0.5 to 3.0 percent, e.g. 0.5 to 1.5 percent.
l Optical brightener in the range of nbout 0 to 2.0, preferably 0.05 to
1. 0 percent, e. g. 0 .15 to 0 . 75 percent .
Enzymes in the rsnge of about 0 to 3 . 0, preferrably 0 . 5 to ~ . 0 percent,
e.g. 0.75 to 1.25 percent.
l 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.
l Coloring dye in the range of about 0 to 4.0, preferably 0.1 to 2.0,
¦ more preferably 0.1 to l.0 percent.
¦ Various of the previously mentioned additives can optionally be added to
¦ achieve the desired function of the added materials.
¦ The hexylene glycol is preferably used with the propylene carbonate.
¦ In the selection of the additives, they will be chosen to be compati~le
~ ith the main constitucnts of the detergent composition. In this applicution,
¦ as mentioned above, all proportions and percentages are by weight of the
entire formlllation or composition unlcss otherwise indicated.
28
~ 7 rl 7 ~
'rhe concentrated nonaqueolls nonionic liquid detergcnt compGsition of
the present invention dispenses readily in the wa~er in the washing machine.
The presently used home ~1ashing machines normally use 2ao to 250 gms of
. powder detergent to wash a full ]oad of laundry. In accordance with the
present invention only 78 cc or 100 gms of the concentrated liquid nonionic
detergent composition is needed.
In an embodiment of the invention the detergen~ con1position of a typical
form~llation is formulated using the below named ingredients:
Weight %
Nonionic surfactant detergent. 30-80
Acid terminated surfactant. 0-20
Phosphate detergent builder salt. 10-60
Hexylene glycol. 5~3~
Propylene carbonate . ~S
Bentone 27. 0-1.5
Arosurf TA 100 0-1.5
Phosphoric acid alkanol ester. 0-1.0
Anti-incrustation agent. 0-10
Anti-redeposition agent. 0-4.0
Alkali metal perborate bleaching agent. 5-15
Bleach activator (TAED). 1.0-8.0
Sequestering agent for bleach. 0-3.0
Optical brightener. 0 . 05-0 . 75
E nzymes. 0.75-1.25
Perfu . 0.1-i.0
~` 29 `
~ I
I I ,o743~1 1
The present in~ention is further illustrated by the follo~ing examples.
EXAMPLE 1
A concentrated nonaqueous liquid nonionic surfactant detergent
composition is formulnt~d from the following ingredients in the amounts
specified .
Weight %
Nonionic surfactant . 37 ~ 7
Acid terminated Dobanol 91-5 reaction product with 5.0
succinic anhydride.
Sodium tri polyphosphate (TPP~. 25
Hexylene glycol. 15
Phosphoric acid alkanol ester. 1. 0
Sodium perborate monohydrate (bleaching agent). ~.0
Tetraacetylethylene diamine (TAED) bleach activstor. 4.5
Anti-redeposition agent (Relatin DM 4096)(1) 1.0
Optical bri8~htener. 0.2
Perfume. 0 . 6
Enzyme (which is Esperase) . 1.
(1) CMC/MC 2:1 mixture of sodium carboxymethyl cellulose and
hydroxymethylcellulose .
The formulation is ground for 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
readily dispersible in water.
. ~ 17!~74~7/1,
_XAMPT,E 2
A concentrated nonaqueous liquid no~ionic surfac~ant d~tergent
composition is fol mulated from th,e fo~lo~ling ingredients in the amounts
specified .
Weight %
Surfact~nt T7. 17
Surfactant T9. 17
Acid terminated Dobanol 91-5 reaction product with succinic
anhydride.
Sodium tri-polyphosphate (TPP). 24.5
Hexylene glycol. 15 . 0
Propylene carbonate . 3
Anti-incrustation agent (Sokalan CP5). 4.0
Phosphoric acid alkanol ester . 1. 0
Sodium perborate monohydriate bleaching agent. 9
Tetraacetylethylene diamine (TAED) bleaching agent . 4 . 5
Sequestering agent for bleach (Dequest 2066). 1.0
Anti-redeposition agent (Relatin DM 4096)(1). 1.0
Optical brighteners (ATS-X). 0.2
Enzyme (~vhich is a protease). 1.0
Perfume . -~
(1) C~lC/MC 2:1 mixture of sodium carboxymethyl cellulose and
hydroxymethylcellulose .
2 5 The formulation is ground for about 1 hour to reduce the particle size
of the suspended builder slllts to less than 40 microns. The formulated
detergent composition is found to be stable and non gelling in storage and
readily dispersible in ~ater.
.
..
~ l 7! ? 7 ~
EXAI\lPLE 3
In order to demonstrate the affect of the flddition of ~lexylene glycol to
nonionic surfactant ~etergent compositions, the formulations A and B were
, prepared and tested to detcrmine yield stress value and plastic viscosity.
A B
Product C nonion;c surfactant.
Sodium tripolyphosphate 30% 30%
Hexy]ene glycol. --- 10 . 5%
Arosurf TA 100 (Quat). 1% 1%
Both formulations were ground for 1 hour to reduce the particle size to
less than 40 microns.
On testing the formulations the following resul~s were obtained.
A B
Yield stress value (Pascal). 15.5 13.0
Plastic viscosity (Pa.s). 0.500 0.265
The above data show that the addition of 10 . 5% hexylene glycol to the
formulation B substantially reduced the plastic viscosity from 5;0 to 2.65,
while reducing the yield stress value from 15.5 to 13.0 Pascal, e.g. by only
about 12 . 9%. The physical stability of the composition was not adversely
affected .
32
~ 17`rJ743~
EXAI\IPLE 4
In order to de~oonstrate the ~ffect of the addition of hexylene glycol
and propylene carbonate on apparent viscosity and on dispersibility of the
nonionic surfactant detergcnt cornpositions the formula~ions C to F werc
prepared and the amount of hexylen~e glycol varied from 0 to 30%.
C(963 D(%) E(%)F(%)
Product C nonionic surfactant . 47 . 9 47 . 9 47 . 3 47 9
Product D nonionic surfactant. 30 20 lO __
Sodium tripolyphosphate.21 21 21 21
l~exylene glycol. -- 10 20 30
Propylene carbonate . . 3 . 3 3 3
Bentone 27. G.8 0.8 0.8 0.8
Each of the formulations were ground for 1 hour to reduce the particle
size to less than 40 microns.
The compositions were tcsted for apparent viscosity and were tested for
dispersibility. The dispersibility test was carried out by pouring 100 gm of
detergent composition in a washing machine dispenser and measuring the
amount of detergent composition remaining in the dispenser after one washing
cycle.
The results obtsined for each of the detergent formulations were as
fol~ows.
C D E F
2G Apparent viscosity (mPa . s) 1350 900 650 530
(LVT, 60 rpm, Sp9)
Dispersibility 24% 17% 7% 5%
(% remaining in dispenser)
The above data show that the addition of 10 to 3096 hexylcne glycol to
the formulutiolls D, E and F substalltially reduces the apparene viscosity and
substalltially in-proves the c~isper~ibility of the formulations. The addition of
33
~ 1 rl 14 ? t`
hexylcl-le ~,lycol or hcxylene ~Iycol and propy]ene carbonate did not cause
any adverse affect on the physical s~ability of the compositions.
The formu1ations of Examples 1 to 4 can be prepared without grinding
. the bllilder snlts and/or s~lsp~nded solid particles to a small particle size,however, best resu]ts are obtaincd by grinding the formulation to reduce the
particle size of the suspended solid particlea.
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
l 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. The
formulations containing suspended builder and solid particles less than 40
microns in size are preferred.
lt is understood that the foregoing detailed description is given merely
by way of illustration and that variations may be made therein without
departing from the spilit of the invention.
3~
