Note: Descriptions are shown in the official language in which they were submitted.
O~OQ6 62301-l4l7
~=1~
(1) Field of Invention
This invention relates to nonaqueous liquid fsbric treating compositions.
More particularly, this invention relates to nonaqueous liquid laundry
de~ergent compositions containing a suspension of a linear condensed,
polyphosphate builder salt in nonionic surfactants which compositions are
stable against phase separation and gelation and are easily pourable and to
the use of these compositions for cleaning soiled fabrics.
(2) Discussion of Prior Art
Liquid nonaqueous hea~y duty laundry detergent compositions are well
known in the art. For instance, compositions of that type muy comprise a
liquid non~onic surfactant in which are dispersed particles of a builder, as
shown for instance in the U.S.P. Nos. 4,316,812, 3,630,9~9 &nd 4,26~,466
and British Patent Nos. 1,205,711, 1,270,040 and 1,600,981.
The related Canadi~n applications assigned to the common assignee are:
: l498,735, ~lled December 30, 1985 describes a nonaqueous liquid
rlonionic surfactant detergent composition comprising a suspension of a
builder salt snd containing an acid terminsted nonionic ~urfactant ~e.g., the
reaction product of a nonionic surfactant and succinic anhydride) to impro~re
dispersibility of the composition in an automatic washing machine.
: ~ 498j815, filed December 31, 1985 describes a nonaqueous liquid
nonionic surfactant detergent composition compr,ising a suspension of builder
salt and containing an alkylene glycol mono-alkyl ether as a v,iscosity and gel
control ngent to improve dispersibility of the compo~ition in an automatic
; ~ wash~ng machine .
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478,380, filed April 4, 1985 describes a nonaqueous liquid nonionic
surfactant detergent composition comp~qsing u suspension of polyphosphate
builder salt and containing an alkanol ester of phosphoric acid to improve
st~bility of the susperlsion against settling in storage.
502,998, filed Feb. 28 , 1986 describes a nonaqueous liquid
nonionic surfact~nt detergent composition comprising a suspension of builder ¦
salt and containing an aluminum stearate to improve stability of the
suspens;on against settling and to improve the yield stress of the composition
while ~t the same time improving or lowering the plastic Iriscosity of the ¦
1 0 composition .
The washing power of synthetic nonionic surfactant detergents in laundry
detergent compositions can be increased by the addition of builders. Sodium
tripolyphosphate is one of the conventionally used bl.~ilders. However, the use of
sodium polyphosphate in dry powder detergents d~es involve several ¦
disadvantages such as, ~or example, the tendency of the polyphosphates to
hydrolyse into pyro- and ortho-phosphstes which represent less valuable
builders.
In addition the sodium tripolyphosphate tends to cake when added to wate
and has a relatively low water solubility and relatively low sequestering cspacity
: 20 :for calcium. I
Liquid detergents are often considered to be more convenient to employ j
than dry powdered or psrticulate products and, therefore, have found
I ~ substantial fsvor with consumers. They are readily 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 lesfi storsge space. Additionally, the ¦
I liquid detergents may have incorporated in their formulations materials which
I ~ could not stand drying operations without deterioration, which materials are ¦
ofterl desirably employed in the manufacture of particulate detergent
products. Although they are posses~ed of many adYantages over unitary or
3l3~
particulate solid products, liquid detergents often have certain inherent
disadvantages ~oo, which have to be overcome to produce acceptab~e
commercial detergent products. Thus, some such products separate out on
storage and others separate out on cooling and are not readily redispersed.
In some cases the product viscosity changes and it becomes either too thick
to pour or so thin as to appear watery. Some clear products become cloudy
and others gel on standing.
The conventionally used sodium tripolyphosphate builder salt has the
disadvantage of tending to degrade in concentrated nonaqueous liquid nonioni
surfactant detergent compositions.
Though hexametaphosphates have been suggested for use in liquid
detergent compositions as builder salts they have not been used because
they are not current raw material and they are expensive. In addition to
the .problem of settling or phase separation the nonaqueous liquid laundry
detergents based on liquid nonionic surfactants suffer from the drawback
that the nonionics tend to gel when added to cold wa~er. This is a
particularly important problem in the ordinary use of European household
sutomatic 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 dispenser is
subjected to a stream of cold water to transfer 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 ~riscosity increases markedly and a gel forms. As a result some of
2 S the composition is not flushed completely off the dispenser during operation
of the machine, and a deposit of the composition builds up with repeated
wash cycles, e~entually requiFing the user to flush the dispenser with hot
water.
The gelling phenomenon can also be a problem whenesTer it is desired to
carry out washing using cold water as may be recommended for certain
synthetic and delicate fabrics or ~brics which can shrink in warm or hot
water.
~I ~3~5~
62301-117
The tendency Or concen~rnted detergent composi~ions to gel dur~ng
storage is aggrav~ted by storing the eompositions in unheated storage areas
or by shipping the compositions durlng wlnter months ln unhea~ed
transportation vehic]es.
Partial solutions to the gelling problem in aqueous substanti~'ly
builder-~ree compositions have been proposed for exarnple by diluting the
liquid noni~nic wi~h eertain viscosity controlling solvent6 and gel-inhibi~ing
agen~s such ~Is ~ower ~Ikanols e. g. ethyl ~cohol (fiee U . S . P. 3 953 380)
alkali metal formates ~nd adipstes (fiee II.S.P. 4 368 147) hexylene glycol
polyethylene glycol etc. and nonionic ~trueture modific~tion and
optimizntion. A~ an example of nonionie 6uraetant modiricatlon one
particu~arly suecessful result ha~ been nehieved by aeidifying the hydroxyl
moi0ty end group of the nonionic molecule. The advantages Or introducing a
carboxylic acid at the end of the nonionie include gel inhibitlon upon sl~lulion;
decreasing the nonionic pour point; and formation of an anionie surfactant when I
neutralized in the washing liquor. Nonionie structure ~ptimization has centered j
on the ehain length of the hydrophobic-lipophilic moiety and the number and
make-~p of alkylene oxide ~e. g. ethylene oxide) unit~ of the hydrophilic moiety.¦
For example it has been ~ound ~hat a C13 fatty aleohol ethoxylated with 8 mole~
Or eth~lene oxide presents only a limited tendeney to gel formation.
Nevertheless improvements are desired in the dispersibility
pourabihty solubility stability and gel inhibition of polyphosphate builder
sa~t nonaqueous liquid nonionie surfaetant fabrie treating eompositions.
BRIEF DESCRIPTION QF THE INVENTION
2$ In aeeordanee with the present invention a highly coneentrated
nonaqueous liquid laundry detergent eomposition is prepared by dispersing a
;~ 10 to 60% by weight of a long lin~ar chain eondensed hexametaphospha~e
: builder salt in 10-60~ by weight of a liq~id nonio~ic surfactant detergen-t.
The long linear chain conde~sed hexane-taphosphate builder salts used
in aceordance with the present invention are known eompounds. The alkali
~ 9
11 ~3~501~; 62301-1417 1
me~al and ammonium Sa~5 of linear condensed hexan~taphosphate ~uilder
s~lts are water soluble.
The linear condensed hex~ osphates used in the present invention
have -the general formula r o
MO-~P-O)~-M
wherein M i8 hydrogen, an alkali metaJ, such aS sodium and pot~ssium, or
Dmmonium cation, and n=20 to 30, preferably about 25.
It is preferred that all of the M'g are alkali metal. A preferred linesr
condensed h~3m~taphosphate is one in which n=25.
In accordance with the present invention it was found t1lat
hexametaphosphate built concentrated nonaqueous liquid nonionic 6urfactant
detergents have improved poursbility and dispersibility as compared to
sodium tripolyphosph~te detergent compositions. The detergent compositions
contnining hexametaphosphates as the principle b~ulder salt do not cske when
added to water and the hexametaphosphates have {I higher water solubilily
than sodium tripolyphosphate. It was further found that the
hexametaphosphate in the concentrsted nonaqueous liquid nonionic surInct~nt
detergent compositions did not tend to degrade while in storage.
The hexsmetaphosphates were ~Iso found to be good anti-scaling and
anti-encrustation ~gents and to prevent calcium crystal growth. The
hexametaphosphates were formed to act in the nonaqueous liquid nonionic
surractant detergent cOmpositionB as superior sequestering agents for
calcium. On gram of hexame~aphospha~e can sequester up to 163 mg. of
calcium as compared to 1 gram of sodium tripolyphosphate which can
sequester up to 111 mg. of crllcium.
In the preferred embodiment of the invention the con ventionally used
sodium tripolyphosphate builder salt is replDced with the a~ali n~
~ e=ameta ~ hate In ti.e detergent ccnEosltions of the present invention
.
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13~}5~ 62301-1417 1
the phosphate b~ulder consisls essen~ially o~ ~he
hexalretaphosphate .
In order to improve the visc~sity characteristic6 of the composition An
acid terminated nonionic surfnc~ant can be added. To further improve the
v~scosity chnracteristic~ of tlle composltion and the storage properties oi the
composition there can be ~dded to the composition viscosity improving and
anti gel agents such alkylene glycol mono alkyl ether6 and anti sellling ¦
~g~nts such ~s phosphoric ~cid esters ~nd ~LIuminum ~tear~te. In prcrerred
embodiment of the invention the detergent composition cont~uns an acid
termin~ted non~onlc surfnctant ~nd/or an ~kylene glycol mono ~Ikyl ethcr
snd ~n llnti seltling agent.
S~niti~ing or bleuching sgents and activa~ors therefor csn be added lo
improve the bleaching and cleansing ch~rac~eristics of the composition.
In an embodiment of the invention the builder components of the
composi~ion are ground to a particle ~ize of less thDn 100 micron6 preferably
less than 40 micr~ns and more preferably less than 10 microns to fur~her
improve the ~tability o the suspension of the builder components in the
liq~lid nonionic surfact~mt detergent.
In addition other ingredients can be added to the composition æuch as
anti-incrustation agents anti-foam agents optical brighteners enzymes
anti-redeposition Agents pe:rfume and dyes.
The presently manufactured washing machines for home use normally
oper~te at washing temperatures up to 100C . Vp to 18 . 5 gallons (7~ liters)
of water are used during the wash and rinse cycles.
About 175gms of powder detergent per wash is normally used.
In accordance with the present invention where the highly concentrated
liquid detergent is used normally only about 100 gms (77 ml) or less of the
liquid detergent composition ls required to wash B full load of dirty laundry.
. I
11 ` 13'~ 6 - l
62301-1417
Accordingly, in one aspect the present invention there is provided ~
liquid heavy duty luundry composition composed of a suspension of an alksli
melal linear condensed he~ametaphosp~te bui1der salt in 1iquia nonionic
surfactQnt . .
According to another aspect, the invention provides a concenlrated
liquid heavy duty laundry detergent composition which is 6table, non-settling
in storage and non-gelling in storage and in use. The liquid compositions of
the present invention are ensily pourable, easily measured ~nd easily put
into the washing machine.
~ccording to anolhcr nspoct, ~ho ~nvon~on provl~lo8 n n)o~ho(l f~r
dispensing a liquid nonionic laundry detergent composition into andlor with
cold w~ter without undergoing gelation. In particular, a method is provided
for filling a container with a n onaqueous liquid laundry detergent composition
in which the detergent is composed, ~t ieast predominantly, of a suspension
of a long linear ch~in condensed polyphosphate in a liquid nonionic sur~ace
active agent and for dispensing the composition from the cont~iner into an
aqueous wash buth, wherein the dispensing i8 effected by directing a stream
of unheated water onto the composition such that the composition is carried
by the stream of water into the wash bath.
ADVANTAGES OVER THE PRIOR ART
The concentrated nonaqueous liquid nonionic sur~actant detergent
compositions containing a long linear chain condensed polyphosphnte builder
sult have the advantages over sodium tripolyphosphate built detergent
composition of h~ving improved pourability and dispersibility of the builder
2S salt, the builder salt does not tend to cake on the addition to water and the
builder salt has a higher water solubility. The compositions of the present
in vention containing , e . g ., alksli metal hexametaphosphate builder salt do
not tend to degrade in the liqu;d nonionic surfactant and exhibit good
anti-scaling and anti-encrustation properties and have u high sequestering
capacity for calcium.
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6230l-l4l7 !
The concentr~ted nonaqueous liqu~d nonionic surf~ctQnt l~undry
detergent compositions of the present invention h~ve the added advant~gcs
of being 6t~ble, non-settling in stornge and non-gelling in storage The
liquid composltions are easily pour~ble, enslly mellsured and essily put into
the l~undry washing machines.
The present inventi~n seeks -to pro~Tide a liquid heavy duty
nonaqueous nonionic detergent composltion containing an alkEii metal
hexnmetaphosphate builder ~lt suspended in a nonlonic surfnctant.
The invention also seeks ~o provide liquid Eabric treating
compositions which are ~uspensions of sn alk~li hexametaphosphate builder
~alt in a nonaqueous l~quid and whlch are storage ~table, easily pourable and
d~spersible ln cold, w~rm or hot w~t~r.
This invention also seeks to formulate a highly built heavy,
15 duty nonaqueous liquid nonionic surf~ct~nt laundry detergent compositions ¦
which can be poured ~t ~11 temperatures and which can be repeatedly
dispersecl from the d~pensing unit of European style autom~tic laundry ~
washing m~chines without fouling or plugg~ng of the dispenser ever during,
the winter months.
This invention also seeks to provide a non-gelling, stable
suspensions of hesvy duty built nonaqueous liquid nonionic l~undry
detergent composition which include an effective amount of an alknli metal
hexametaphosphate builder salt.
This invention further seeks to prov.ide non-gelling, s~able
25 suspension6 of heavy duty built nonsqueous liquid nonionic laundry ¦
detergent composition which include an amount of phosphoric acid alkanol ¦
ester and/or oluminum f~tty flcid ~nlt ~nti-settling agent which is ~ufficient
to incre~se the st~bility of the composition, i.e. prevent settling of builder
particles , etc ., preferably while reducing or at least without increasing the
30 plastic viscosity of the composition.
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~31C~Si0~6
62301-1417
The invention will become more ~pparent from the
following detailed de~cription of preferred embodiments are
generally provided for by preparing a detergent composltion by adding to a
nonaqueou6 liquid nonionic surfnctant an effective amount of an alknli metal
hexametaphosphate bulldar salt and inorganlc or organlc fabric treating
additives, e. g. viscoslty improving and anti-gel agents, anti-~ettling ~gents,
anti-incrustation agents, ble~ching agent6, bleach activator6, antl-fonm
agent~, opticel brighteners, enzyme6, ~mtl-redeposition agents, perfume and
dye~ .
Nonionic Surfactant Deter~ent
The nonionic synthetic organic detergent~ employed in the practice of
the invention m~y be any of a wlde variety of such compounds, which are
well known.
As is well known, the nonionic synthetic org~nic detergents ~re
characterized by the presence of an organic hydrophobic group and an
organic hydrophilic group and are typically produced by the condensation of
an organic aliphntic or alkyl aromatic hydrophob~c compound with ethylene
oxide (hydrophilic in nature). Practically any hydrophobic compound having
a carboxy, hydroxy, amldo or amino group with a free hydrogen attached to
l the nltrogen can be condensed wi~h ethylene ox~de or with the polyhydrstion
product thereof, polye~hylene glycol, to form a nonionic deter~en~. The
lenglh of the hydrophllic or polyoxy ethylene ch~in c~ be readily ndjusted
to achieve the desired balance between the hydrophobic and hydrophilic
groups . Typical suitable nonionic surfactants are those disclosed in U . S .
patents 4,316,~12 and 3,630,929,
Usually, the nonionic detergents are poly-lower alkoxylated lipophiles
wherein the desired hydrophile-lipophlle bnlance i8 obtained from addition of
a hy~rophilic poly-lower alkoxy group to a lipophilic moiety. A preferred
class of the nonionic detergent employed 18 the poly-lower alkoxylated higher
alkanol wherein the alkanol is of 9 to 18 carbon atom6 and wherein the
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number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to
12 Of such mateFials 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 5 to 8 or 5 to 9 lower alkoxy groups per mole.
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.
Exemplary of such compounds are those wherein the alkanol is of 12 to
q~ 15 carbon atoms and which contain about 7 ethylene oxide groups per mole,
10 ~ ¦ e.g. Neodol3~2S-7 and Neodoi~3-5.5, which products are made by Shell
¦ Chemical Company, Inc. The former is a condensation product of a mixture
¦ of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7
moles of ethylene oxide and the latter is-a corresponding mixture wherein the
carbon atom content of the higher fatty alcohol is 12 to 13 and the number
of ethylene oxide groups present averages about 6 . 5 . The higher alcohols
are primary alkanols.
Other examples of such detergents include Tergitol 15-S-7 and Tergitol
15-S-9, both of which are linear secondary alcohol ethoxylates made by
Vnion Carbide Corp. The former is mixed ethoxylation product of 11 ~o 15
carbon atoms linear secondary alkanol with seven moles of ethylene oxide and
the latter is a similar product but with nine moles of ethylene oxide being
reacted.
Also useful in the present composition as a component of the nonionic
detergent are higher molecular weight nonionics, such as Neodol 45-11,
which are similar ethylene oxide condensation products of higher fatty
alcohols 9 with the higher fatty alcohol being of 14 to 15 carbon atoms and
the number of ethylene oxide groups per mole being about 11. Such products
are also made by Shell Chemical Company.
Other useful nonionics are represented by the commercially well known
class of nonionics sold under the trademark Plurafac. The Plurafacs are the
~k ~r~e~ k
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reaction product of a higher linear alcohol and a mixture of ethylene and
propylene oxides, containing a mixed chain of ethylene oxide and propylene
o~dde, terminated by a hydroxyl group. Examples include Product A (a
C13-C15 fatty alcohol condensed with 6 moles ethylene oxide snd 3 moles
propylene oxide), Product B (a C13-C15 fatty alcohol condensed with 7 moles
propylene oxide and 4 moles ethylene oxide~, and Product C (a C13-C15
fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene
oxide) .
Another group of liquid nonionics are commerci~lly available from Shell
Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 is an
ethoxylated Cg-C11 fatty alcohol wi~h an a~rerage of 5 moles ethylene oxide
and Dobanol 25-7 is an ethvxylated C12 C15 fatty alcohol with an average of
7 moles ethylerle o~nde per mole of fatty alcohol.
In the preferred poly-lower alkoxylated higher alkanolsg to obtain the
15 ~ best balance of hydrophilic and lipophilic moieties the number of lower
alkoxies will usually be from 40% to 10û% of the number of carbon atoms in
the higher alcohol, preferably 40 to 60~6 thereof and the nonionic detergent
will preferably contain at least 50% of æuch preferred poly-lower ~lkoxy
higher alkanol. Higher molecular weight alkanols and va~ous other normally
solid nonionic detergents and surface active agents may be contributory to
gelation of the liquid detergent and consequently, will preferably be omitted
or limited in quantity in the present compositions, although minor
proportions thereof may be employed for their cleaning properties, etc. With
respect to both preferred and less preferred nonionic detergents the alkyl
groups present therein are generally linear although branching may be
tolerated, such as at a carbon next to or two carbons removed from the
terminal carbon of the straight chain and away from the ethoxy chain, if
:: :
such branched alkyl i~ not more than three carbons in length. Normally,
~he proportion of carbon atoms in such a branched conffguration will be
~, minor rarely exceeding 20% of the total carbon atom content of the alkyl.
~, ~ 11
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Similarly, ~though linear allcyls which are terminally j~ined to the ethylene
oxide chains are highly preferred and are considered to result irl the best
combination of detergency, biodegradability and non-gelling characteristics,
mediPI or secondary joinder to the ethylene oxide in the chain may occur. It
is usually in only a minor proportion of such alkyls, generally less than 20%
but, as is in the cases of the mentioned Terigtols, may be greater. Also,
when propylene oxide is present in the lower alkylene oxide chain, it will
uæually be less than 20% thereof and preferably le~;s than 1096 thereof.
When greater proportions of non-terminally alkoxylated ~lkanols,
propylene oxide-containing poly-lower alkoxylated alkanols and less
hydrophile-lipophile balanced nonionic detergent than mentioned above are
employed and when 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 controlling
compounds of the invention can also improve the properties of the detergents
based on such nonionics. In son-e cases, as when a higher molecular weight
poly lower alkoxylated higher alkanol is employed, often for its detergency,
the proportion thereof will be regulated or limited 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 necessary to utili2e the higher molecular weight
non~onics for their detergent properties sinee the preferred nonionics
describsd herein are excellent detergents and ~dditionally, permit the
attainment of the desired viscosity in the liquid detergent without gelation at
low temperatures.
Another useul group of nonionic surfactants are the "Surfactant T"
series of nonionics available from British Petroleum. The Surfactant T
nonionics are obtained by the ethoxylation of secondary C 13 fatty alcohols
having a narrow ethylene oxide distFibution. The Surfactant T5 has an
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l~S~ 62301.-1417
aversge of 5 moles of ethylene oxide; Surfactant T7 an average of 7 moles of
ethylene oxide; Surfactant T9 an average of 9 moles of ethylene oxide and
Surfactant T12 an average of 12 moles of ethylene oxide per mole of
secondary C13 fatty alcohol.
S In the compositions of this invention, preferred r~onionic surfactants
include the C13-C15 secondary fatty alcohols with relatively nsrrow 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 moles ethylene oxide.
Mixtures of two or more of the liquid nonionic surfactants can be used
and in some cases advantages can be obtained by the use of such mixtures. I
Acid Terminated Nonionic Surfactant
The viscosity and gel properties of the liquid detergent eompositions ¦
can be impro~red by including in the composition an effective amount an ac;d
terminated liquid nonionic surfactant. The aeid terminsted nonionic ¦
1~ 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 esSer of a nonionic surfactant and a
polycarboxylic acid or anhydride.
As disclosed in the eommonly assigned C~nadian applieation Serial No.
478,379 filed April 4, l9g5,
the free carboxyl group modified nonionic surfactants, which may
be broadly charaeterized as polyether carboxylic acids, funetion to lower the j
temperature at which the liquid nonionie forms a gel with water.
The addition of the acid terminated nonionic surfactants to the liquid
nonionic surfactant aids in the dispensibility of the eomposition, i . e .
pourability, and lowers the temperature at which the liquid nonionic
surfaetants form a gel in water without a decrease in their stability against
settling. The acid terminated nonionie surfaetant reaets in the washing
machine water with the alkalinity of the dispersed builder salt phase of the
detergent eomposition and acts as an effeetive anionic ~urfaetant.
13
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Specific examples include the half-esters of Pluraf~c RA30 with succinic
anhydride, the ester or h~lf ester of Dobanol 25-7 with succinic anhydride,
and the ester or half ester of Dobanol 91-5 with succinic anhydride. Instead
of succinic anhydride, other polycarboxylic acids or anhydIqdes can be used,
e.g. maleic acid, maleic acid anhydride, citric acid ~nd the like.
The acid terminated nonionic surfactants can be prepared as follows:
Acid Term;nated Product A. 400 g of Product A nonionic surfactant
which is a C13 to C15 alkanol which has been alkoxylated to introduce 6
ethyleneoxide 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 ~o remove unreacted succinic material. Infrared analysis
indicated that about one half of the nonionic surfactant has been converted
to the acidic half-ester thereof.
- . Acid Terminated Dobanol 25-7. 522 g of Dobanol 25-7 nonionicsurfactant which is the product of ethoxylation of a C12 to C15 alkanol and
has about 7 ethyleneoxide units per molecule of alkanol is mixed with 100g of
succinic anhydride and 0, lg of pyridine (which acts as an esterification
catalyst) and heated at 260C for 2 hours, cooled and filtered to remove
unreacted succinic material. Infrared analysis indicates that substantially all
the free hydroxyls of the surfactant have reacted.
Acid Terminate Dobanol 91-5. 1000 g of Dobanol 91-5 nonionic
surfactant which is the product of ethoxylation of a Cg to Cll alkanol and
has about 5 ethylene a~de units per molecule of alkanol is mixed with 265g
of succinic anhydride and 0.1g of pyridine catalyst and heated at 260C for
; 25 2 hours, cooled and filtered to remove unreacted succinic material. Infrared
analysis indicates that substantially all the free hydroxyls of the surfaetant
have reacted,
Other esterification catalysts, sueh as an alkali metal alkoxide (e. g.
sodium methoxide) may be used in place of, or in admixture with, the
I pyridine. 14
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13(;~50~6 G2301-1417
The ncidic polyether compound, i. e . the acid Sermina~ed nonionic
surf~ctnnt is prererably added dissolved in the nonionic surfMctant.
DETAILED D~SCnlPTlON OF INVENTION
The liquid nonaqueous nonionic surfactant used in the compositions Or
the present invention has dispersed and suspended ~herein fine particles c,r
inorganic andlor organic detergent builder sDlts.
The present invention includes as an essential part of the composition
long linear chain condensed l~taphosphate builder s, lts.
The long linear chain condensed hexalretaphospllate bui1der salts used
in the detergent ca[~?ositions oE the present invention have the Eoll~wing
general formula r I 1
MO-~P-O~-M
wherein ~,~ is a member selected from the group consisting of hydrogen,
alkali metal and ammonium cation, and n-20 to 30, pre~errably about 25. ~ll
the M's are preferral~,]y alkali metQls or ammon~um , e . g., 60dium and
pot~sslum, with sodium being the more preîerred. A preferred builder salt
is the nlkali metal or ammonium hexametaphosphate.
A specific example of a linear condensed he~Tetaphosp~ate builder
salt thalt can be used is
. . _11 .
NaO- ~P-O In-N~
O n=~5
N a
The detergent compositions containing alkali metal hexnmetaphosphstes
provide improved cleaning per~ormance. For example, B 100 gm ~77 cc~ ol
29.6% concentration of sodium hexametaphosphate provide~ cleaning
performance equivalent to 100 gm (77 cc) of 309~ sodium tripolyphosphate
built detergent .
The invention detergent compositions include water 601uble nnd/or water
insoluble detergent builder salts. Water soluble inorgan'ic slkaline builder
salts which can be used alone w1lh the dè~ergent compound or in ndm1xture
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~\~ ~3~ n~ - I
with other builders are alkali metal carbonates, bicarbon~tes, borates,
phosphates, polyphosphates, and silicates. (Ammonium or substituted
ammonium salts can ~lso be used. ) Examples of conventionally used builder
salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate,
sodium pyrophosphate, potassium pyrophospha~e, sodium bicarbonate,
potassium tripolyphosphate, sodium and potassium bicarbonate. Sodium
tripolyphosphate (TPP) is a commonly used builder salt.
The alka)i metQl silicates are u8ef~ builder salts which also function to
adjust or control the pH and to make the composition anticorrosive to washin~
machine parts. Sodium silicates of Na2OISiO2 ratios of from 1,6/1 to 113,2,
especially about 1/2 to 1/2 ,8 are preferred. Potassium ~ilicates of the same
ratios can also be used. A preferred alkali metal silicate is sodium
disilicate. -
Since the compositions of this invention are generally highly
concentrated, and, therefore, may be used at relatively low dosages, it can
be desirable to supplement the long linear ehain condensed polyphosphate
¦ builder with an auxiliary builder such as an alkali metal lower polycarboxylic
acid having high calcium and magnesium binding capacity to inhibi~
incrustation which could otherwise be caused by formation of insoluble
~; 20 calcium and m~gnesium salts. Suitable alkali metal polycarboxylic acids are !
alkali metal salts of citric and tartaric acid, e.g., monosodium citrate I
(anhydrous), t~ssodium citrate, glutaric acid salt, glutonic acid salt and ¦
diacid salt with a longer chain. ~ I
Other organic builders are polymers and copolymers of polyacrylic acid,
2~ and polymaleic anhydride and the alkali metal salts thereof. More specifically
such builder salts can consist of a copolymer which is the reaction product !
of about equal moles of methacrylie acid and maleic anhydride which has been !
completely neutralized to form the sodium sAlt thereof. The builder is
commercially available under the tradename of Sokalan CP5. This builder
~erves when used even in small amounts of inhibit incrustation.
16
~ .
. ~
~ 1l 62301-t~17
~31~S0(:1~
Ex~mples of organic alkaline sequestrant builder salts which can be
used with the detergent builder s~lts or in admixture with other organ;c ~nd
inorganic builders are slk~li metal, ammonium or substituted ammonium,
aminopolycarboxylates, e. g. sodium and potsssium ethylene
diaminetetra~eatate (EDTA), sodium and potassium nitrilotriucetates (N'TA),
and triethanolammonium N-(2-hydroethyl)nitrilodiacet~tes. Mixed salts of
these aminopolycarboxylates are also suitable.
Other organic builders include the polyacetal carboxylates. The
polyacetal carboxylates and their use in detergent compositions are described
in Canadian application No. 516,246 filed Augu~t 19, 1986, assigned to
applicants' assignee and in a U.S.P. No~. 4,144,226 4,315,092 and 4,146,495.
Other typical suitable builders include, for example, ~hose disclosed in
U.S. Patents 4,316,812, 4,264,466 and 3,630,929, The inorganic alkaline
buil~er salts can be used with the nonionic surIact~nt detergent compound or
in admixture with other organic or inorgsr~ic builder salt~.
The water insoluble crystalline and amorphous aluminosilicate zeolites
can be used. The zeolites gener~lly have the formula
(M20)X (A1203)~ ~SiO2~Z WH2
wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5
l or higher and preferabiy 2 to 3 and w is from 0 to 9, prefersbly 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 aluminos31icates have
calcium ion exchange capacities of about 200 milliequivalents per gram or
greater, e.g. 400meq lg.
Various crystalline zeolites (i.e. alumino-silicates) that can be used are
described in British Patent 1,504,168, U.S.P. 4,~09,136 and Canadian
Patents 1,072,835 and 1 > 087,477.
An example of amorphous zeolites useful
- 30herein can be found in Belgium Patent 835,351 .
' . 1~,
`'' h~
~ ~L3~ )6 - I
Other materials such as elays, particularly of the water-insoluble types,
may be useful adjuncts in compositions of this invention. Particularly useful
is bentonite. This 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 hydrogen, sodium,
potassium, calcium, etc., may be 1008ely combined. The bentonite in its
more purified form (i . e . free from any grit, sand, etc . ) suitable for
detergents eontains at least 50~ montmorillonite and thus its cstion exchange
eapaeity is ~t least about 50 to 75 meq per 100g of bentonite. Particularly
preferred 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 desclqbed in British Patent 401,413
to Marriott and British Patent 961,221 to Marriott and Guan.
Viscosity Control and Anti Gel A~ents
1~ The inclusion in the detergent composition of an effective amount of low
moleculsr weight amphiphilic compounds whieh funetion as ~iscosity control
and gel-inhibiting agents for the nonionic surfaetQnt substantially improves
the storage properties of the composition. The ~mphiphilic compounds can
be considered to be analagous in ehemieal ~trueture to the ethoxylated
and/or propoxylated fatty alcohol liquid nonionie surf~ctants but have
relatively short hydrocarbon chain lengths SC:~ to CE~) and a low content of
ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).
Suitable amphiphilic compounds can be represented by the following
general formula
RO(CH2CH2O)n
where R is a C2-58 alXyl group, and n is a number of from about 1 to
6, on average.
Specifie~lly the compounds are lower (C2 to C3~ alkylène glyeol mono
lower (C2 to C5) alkyl ethers.
~ ~r~e~
18
, .
- , ` - - .
,
~ 62301-1417
~ 3(~51)06
More specifically the compounds are mono di- or tri lower (C2 to C3)
alkylene glycol mono lower (Cl to C5) alkyl ethers.
Specific examples of suitable amphiphilic compounds include
ethylene glycol monoethyl ether (C2H5-0-C132CH20H),
diethylene glycol monobutyl ether (C4Hg-O-(CH2CH20)2H),
tetraethylene,glycol monobutyl ether (C4H7-0-(CH2CH20),1H) ~d
dipropylene glycol monomethyl ether (CH3-0-(CH2CHO)2H.
Diethylene glycol monobutyl ether is especially preferred.
The inclusion in the composition of 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 stabili~y against settling
and improves the dispersibility of the composition on the sddition to warm
wster or cold water.
The compositions of the present invention have improved viscosity and
15' stability chsracteristics and remain stable and pourable at tempera~ures as .
low as about 5C and lower.
Stabilizing Agent~
In an embodiment of this invention the physicsl stability of the
suspension of the detergent builder compound or compounds and~ sny other
suspended add~itive, such AS bleaching agent, etc., in the liquid vehicle is
improved by the presence of a stabilizing agent which is an slkanol ester of
phosphoric acid or an aluminum salt of a higher fatty acid.
Improvements in stability of the composition may be achieved in certsin
~; ~ formulations by incorporation of a small effective amount of an scidic organic
phosphorus compound having an acidic - POH group~ such as a partial ester
of phosphorous acid and an slkanol.
" As disclosed in the commonly assigned Canadian application Serial No.
478, 379 filed April 4, 198 5,
~he acidic organic phosphorus compound having an acidic POII
~9
62301~1417 ~
` 13~ 6
group can increase the st~bility of the suspension of builders irl the
nonaqueous liquid nonionic surfact~nt.
The acidic organic phosphorus compound may be, for instance, a partial
ester of phosphoric acid snd ~n alcohol such as an ~ anol which hss A
5lipophilic 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 (Empiphos 5632 from Marchon); it is made up of about 35%
monoester and 65% diester.
10The inclusion of quite small amount~; of the acidic organic phosphorus
compound maXes the suspension significantly more stable again6t settling on
standing ~ut remains pourable, while, for the low concentration of stabilizer, I
e.g. below about 1%, its plastic viscosity will generally decrease. I
Further improvement~ in the stability and a~ti-settling properties of the
15composition msy be achieved by the addition of a small effectilre amount of analuminum salt of a higher fatty acid to the composition.
'rhe aluminum salt stabilizing agents are the subject matter of the
commonly assi~ned Canadian application SeriAI No, 502,998, ~iled
Feb. 28, 1986.
20The preferred higher aliphatic fatty acids will have from about 8 to
about 22 carbon atoms, more preferably from about 10 to 20 carbon atoms,
and especially preferably from about 12 to 18 carbon atoms. The aliphatic
radical may be saturated or unsaturated and may be straight or branched.
As in the case of the nonionic surfactants, mixtures of fstty acids may also
25be used, such es those derived from natural source~, such as tallDw fatty
acid, coco fatty acid, etc.
Examples of the fatty acids from which the aluminum salt stabilizers can
be formed include, decarJoic acid, dodecanoic ~ci~, palmitic acid, myristic
acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coco fatty
acid, mlxtures of these acids, etc. The aluminum salts of these acids are
;P ~
~ ~3(~50C~
generally commercially available, and are preferably used in the triacid form,
e. g. aluminum stearate as aluminum tristearate Al(C17H35C00)3 . The
monoacid salts, e.g. aluminum monostearate, Al(OH)2(C17H35COO) and
diacid salts, e.g. aluminum distearate, Al(OH~ICl7H35C00)2, and mixtures
S of two or three of the mono-, di- and triacid aluminum salts can also be
used. It is most preferred, however, that the triacid aluminum salt
comprises at least 30%, preferably at least 50%, especially preferably at least
80% of the total amount of aluminum fatty acid salt.
The aluminum salts, as mentioned abov2, are commercially av~ilable and
can be essily produced by, for example, saponifying a fatty acid, e. g.
animal fat, stearic acid, etc., followed by treatment of the resulting soap
with alum, alumina, etc.
Although applicants do not wish to be bound by any particulàr theory
- of the manner by which the aluminum salt functions to prevent settling of
the suspended particles, it is presumed that the ~luminum salt increases the
wettability of the solid surfaces by the nonionic surfactant. This increase in
wettability, therefore, allows the suspended particles to more easily remain
in suspension.
Only very small amounts of the Pluminum sslt stabilizing agent i6
required to obtain the significant improvements in physical stability.
In addition to its action as a physical ~tabilizing agent, the aluminum
- salt has the additional advantages over other physical stabilizing agents that
it is non-ionic in character and is compatible with the nonionic æurfactant
component and does not interfere with the overall detergency of the
composition; it exhibits some anti-foaming effect; it can function to boost the
activity of fabric softeners, and it confers a longer relaxation time to the
suspensions .
Bleaching A~ents
The ~leaching agents are classified broadly, for convel ience, as
chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by
21
, , I
' - .
-
:~L3~5io~6 6230~-1417
sodium hypochlori~e (NgOCl), potgssium dichloroisocyanurate (59% availsble
chlorine), and trichloroisocyanuric acid (95% a~ailable chlorine), Oxygen
ble~ches are preferred and are represented by percompou~ds which liberate
hydrogen peroxide in so~ution. Preferred exsmples include sodium a~d
potsssium perborates, percarbonates, and perphosphates, and potassium
monopersulfate. The perborates, particularly sodium perborate monohydrate,
are especiully preferred.
The perpxygen cc~mpound is preferably used in admixture with an
activator theref~r, Sui~able actiYators which can lower the efective
operating temperature of the peroxide bleaching agent are disclosed, for
example, in U.S.P. 4,264,466 or in column 1 of U.S.P. 4,430,244.
Polyucylated compounds are preferred ac~ivators; among these, compounds
such as tetraacetyl ethylene diarnine ("TAED") and pentascetyl glucose are
particularly preferred.
Other useful activators include, for example, acetyls01icylic acid
derivatives, ethylidene benzoste acetate and its salts, ethylidene carboxylate
acstate and its sslt~, alkyl and ~1kenyl succinic anhydride,
tetraacetylglycouril t"TAGUn), and the derivatives of these. Other useful
classes of activators are disclosed, for example, in ll.S.P. 4,111,826,
4,422,950 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 resction between such peroxyacid and hydrogen pero~nde in the
w&sh solution in the presence of metal ions.
Suitable sequestering agents for this purpose include sodium salts of
nitrilotriacetic acid (NTA), ethylene diamine tetraacetic scid (EDTA),
diethylene triamine pentaacetic acid (DETPA), diethylene triamjne
pentamethylene phosphonic acid (DTPMP) ~old under the trademark Dequest
22
gv ~
~L3VS~Q~6 62301-141;
2066; and ethylene diamine te~I~amethylene phosphonic acid ~EDITEMPA).
The sequesterir~g ager~s can be used ~one or in adm;xture.
In order to avoid loss o peroxide bleaching agent, e. g. sodium
perborate, resulting from enzyme-induced decomposition, such as by cst~l~se
en~yme, the compositions may ~ddition~ly 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.
Of speci~l interest as the inhibitor compound, mention can be made of
hydroxylamine sulfate and other water-soluble hydroxylamine s~lts. In the
preferred nonaqueous compositions of this invention, suit~ble smounts 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 examp]e, 0.1 to 10%, by weight of the composition.
In addilion to the detergent builders, various other detergent additives
or adjuv~nts may be present in the detergent product to give it ad~itional
desired properties, either of functional or aesthe~ic n~ture. Thus, there
may be included in the formulation, min~r amounts of 60il 6uspending or
anti-redeposition agents, e.g. poly~rinyl alcohol, fatty amides, sodium
csrboxymethyl cellulose, hydroxy-propyl methyl cellulose. A preferred
anti-redeposition agent is sodjum carboxymethyl cellulose ha~ing a 2 :1 rstio
of CM/MC which is sold under the trade.mark Relatin DM 4050.
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 j benzidene sulfone, etc., most preferred
are stilbene ~nd triszole combin~tions. Preferred brighteners are Stilbene
Brightener *N4 which is a dimorpholino diarlilino stilbene sulfonate and
Tinopal*ATS-X which is well kn~wn in the art.
.
*Trade-mark 23
~3~5~0~ j
Enzyrnes, preferably proteolytic enzymes, such as subtilisin, bromelin,
papain, trypsin and pepsin, as well as amylase type anzymes, lipase type
enzymes, and mixtures thereof can be used. Preferred enzymes include
protease slurry, esperase slurry and amylase. A preferred enzyme is
5A Esperse SL8 which is a protease. Anti-~oam agents, e.g. silicon compound6,
such as Silicane L 7604 can also be added in small effective arnounts.
Bactericides, e. g. tetrachlorosalicylanilide and hexschlorophene,
fungicides, dyes, pigment~ (water dispersible), preservatives, ultraviolet
absorbers, anti-yellowing agen~s, such as sodium carboxymethyl cellulose,
pH modifiers and pH buffers, color safe bleaches, perfume, and dyes and
bluing agents such as ultramarine blue can be used.
The composition may also contain an inorganic insoluble thickening agent
or dispersant of very high surface area such as finely divided silica of
extremely fine particle size (e . g. of 5-100 mîllimicrons diameters such as sold
under the name Aerosil~or the other highly voluminous inorganic carrier
materials disclosed in U.S.P. 3,630,929, iD proporffons of 0.1-10%, e.g. 1 to
5%. It is preferable, howeYer, that compositions which form peroxyacids in
the wash bsth (e. g. compositions containing peroxygen compound and
activator therefor) be substantially free of such compounds and of other
silicates; it has been found, for inst~nce, thst silica and silicates promote
the undesired decomposition of the peroxyacid.
In an embodiment of the invention the stability of the builder salts in
the composition during storage and the dispersibility of the composition in
water is improved by grinding and reducing the particle size o~ the solid
builders to less than 100 microns, preferably less than 40 microns and more
preferably to less than 10 microns. The fiolid builders are generally
supplied in particle sizes of about 100, 200 or 400 microns, The nonionic
~; liql~id surfactant phase can be mixed with the solid builders prior to or after
carrying out the grinding operation.
,~ 6le~ k^
2~
., ~ . L
:13~5~0~
In a preferred embodiment o the invention, the mixture of liquid
nonionic surfactant and solid ingredients is subjected to an att~tion type of
mill in which the particle sizes of the solid ingredients are reduced to less
than about 40 microns, preferrably to less than about 10 microns, e . g. to an
S average particle size of 2 to 10 microns or even lower (e. g. 1 micron) .
Preferably less than about lO96, especially less than about 5% of all the
suspended particles have particle si%es greater than 10 microns.
Compositions whose dispersed particles are of such small size have improved
stability against 6eparation or settling on gtorage. Addition of the acid
terminated nonionic surfactant compound aids 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
ingredients be high enough (e . g . at least about 40% such as about 50%) that
the solid particles a~e in contact with each other and are not substantially
shielded from one another by the nonionic surfactant liquid. After the
grinding step any remaining liquid nonionic surfactant can be added to the
ground formulation. Mills which employ grinding balls (ba~l mills) or similar
mobile g~nding elements have given very good results. Thus, one may use
a ~aboratory bstch attritor having 8 mm diameter steatite grinding b~lle. For
larger scale work a continuously operating mill in which there are 1 mm or
1.5 mm diameter grinding balls working in a very smal~ gap between a stator
and a rotor operating at a relatively high speed (e.g. a CoBall mill) may be
employed; when using such a m~l, it is desirable to pass the blen~ of
25 ~ nonionic surfactant ~nd solids first through a mill which does not effect such
fine grinding (e.g. a colloid mill) to reduce the particle gize to less than 100microns (e . g~. to about 40 microns) prior to the step of g~nding to an
~, average particle diameter below about 10 microns in the conffnuous ball mill.
In the preferred heavy duty liquid laundry detergent compositions of
the invention, typical proportions (percent ba9ed on the total weight of
composition, unless otherwise specified) of the ingredients are as follows:
!l l
~L3C~SO~i 62301-1417 i
Liquid nonionic surf~ctant detergent in the range of nbout 10 to 60,
such as 20 to 50 nnd 30 to 40 percent.
Acid ~erminllted nonionic surfactant may be omitLed, it i6 preferred
however that it be added to the composition in sn amount in the range of
sbout 0 to 30, such as 5 to 25 snd 5 to 15 percent.
Long linear chain condensed hexa~et~aphosp~at-~ builder salts in the range
of about 10 ts~ 60, such as 20 to 50 ~nd 25 to 35 peraent.
Copolymer of polyacrylate and polymaleic anhydride slkali metal 6alt anti
encrustation agent in the range of about 0 to 10, such as 2 to 8 and 2 to 6
percent .
Alkylene glycol monoalkylether anti-gel agent in Qn amount in the range
Or about 0 to 20, such as 5 to 15 and 8 to 12 percent.
Phosphoric ~cid alkanol ester stQbilizing agent in the range of 0 to 2.0
oP 0 .1 to 2 . 0, such as 0 .10 to 1. 0 percent .
Aluminum salt of fatty scid stabilizing ugent in the range of about 0 to
3 . 0, such as 0 .1 to 2 . 0 nnd 0 . 5 to 1. 5 percent .
It is preferred that at lesst one of phosphoric ~cid ester or aluminum
salt stabilizing agents be included in the composition.
Blesching ~gent in the range of about 0 to 35, 6uch ~8 5 to 30 and 8 to
20 15 percent.
Ble~ch sctivator in the range of ~bout 0 to 20, such a~ 1 to 15 and 2 to
6 percent.
Sequestering agent for bleach in the range of about 0 to 3.0,
preferabl~ 0 . 5 to 2 . 0 snd O . 5 to 1. 5 percent .
25Anti-redeposition agent in the range of about 0 to 3 . 0, such ss 0 . 5 to
2 . 0 and 0 . 6 to l . 5 percent .
OptiCPI brightener in the range of about 0 to 2, û, such as 0 . 05 to 1. 5
and 0 . 3 to 1. 0 percent .
Enzymes in the range of about 0 to 3.0, ~uch as 0.5 to 2,0 And 0.5 to
30I . 5 percent .
26
:':
.~
.
- ~lL3~50l~
.
Perfume in the range of about 0 to 2.0, such as 0.10 to 1,25 and 0.5 to
1.0 percent.
Dye in the range of about 0 to 1.0, such as o.o~as to 0.050 and 0.0025
to 0.0100 percent.
~arious of the previously mentioned additives eQn optionally be added to
achieve the desired function of the added materials.
Mixtures of the scid term;nated nonionic surfsctant and the alkylene
glycol alkyl ether anti-gel agents can be used and in some cases advantages
can be obtained by the use of such mixtures alone, or with the addition to
the mixture of a stabilizing and anti settling agent, e.g. phosphoric acid
alkanol ester.
In the selection of the additives, they will be chosen to be eompatible
with the main constituents of the detergent composition. In this application,
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 washing machines normally use 25D gms of powder
detergent to wash a full load of laundry . In accordance with the present
invention only about 77 ml or about 100 gms of the concentrated liquid
nonionic detergent composition is needed.
In a preferred embodiment of the invention the detergent composition of
a typical formulation is formulated using the below named ingredients:
Weight %
Nonionic surfactant detergent 30-40
Acid terminated nonionic surfactant 5-15
Alk~li metal hexametaphosphate 25-35
Anti-encrustation agent (Sokalan S: P-5) 0-10
Alkylene glycol monoalkyl ether 8-12
Alkanol phosphoric acid ester (Empiphos 5632) 0.1-1.0
27
`:
~ - .
~3~S~(~6 - I
Anti-redeposition agent (Relatine DM 4050) 0-3. 0
Alkali metal perborate bleaching agent 8-15
Bleach activator (TAED~ 2-6
Sequestering agent (Dequest 2066~ 0-3.0
Optical brightener (ATS-X) 0.05-1.0
Erlzymes ~Protease-Esperase SL8) 0.5-1.5
Perfume 0 . 5-1. 0
The present invention iæ further illustrated by the following example.
EXAMPLE 1
A concentrated nonaqueous liquid nonionic surfactant detergent
composition i5 îormulated from the following ingredients in the amounts
specified .
Weight %
A mixture of C13-C 5 fatty alcohol condensed with 7 moles of
propylene oxide an~ 4 mdes ethylene oxide and C -C15 fatty
alcohol condensed with 5 moles propylene oxide an~3 10 moles
ethylene o~ade 15.5 ¦ .
Surfactant T 7 9 . 0
Surfactant T 9 ~, 0
Acid terminated Dobanol 91-5 reaction product with
succinic anhydride 6.0
Sodium hexametaphosphate 29 . 6
Diethylene glycol monobutyl ether 9.0
Alkanol phosphoric acid ester (Empephos 5632) 0.3
Anti-encrustation agent (Sokalan CP-5) 3 . O
Sodium perborate monohydrate bleaching agent 10.0
Tetraacetylethylene diamine (TAED) bleach activator~.5
Sequestering agent (Dequest 2066) 1.0
Optical brightener (Tinopal ATS-X) 0.5
Anti-redeposition agent ~Relatin DM 4û50) 1.0
Esperase slurry (Esperase SLB) 1.0
Perfume 0 . 5925
Dye
28 100.08
. .. ,~
~3(;~S0~6
The formulation is ground for about l hour to reduce the particle size
of the suspended bui~der salts to less than 40 microns. The formulated
detergent composition is found ~o be stable and non-gelling in storage and to
have a high detergent capacity.
The formulations can be prepared without grinding the builder salts and
suspended solid particles to a small partlcle 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 SP1t6 and
suspended solid particles can be ground or partially ground prior to mixing
them with the nonionic surfactant. The g~inding 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 lOn
microns in size are preferred.
EXAMPLE 2
In order to demonstrate the effec~ on cleaning and anti-encrustation or
anti-scPling performance of the substitution of sodium tripolyphosphate by
sodium he~ametaphosphate detergent builder sslt of the present invention,
the detergent composition formulation of Example 1 containing 29.6% by
weight of sodium hexametaphosphate is compared in repeated laundry washing
machine cycles with the same composition in which the hexametaphosphate
is replaced with 30% by weight of sodium tripolyphosphate.
The repeated wash cycles are carried out at laundry wash water
concentrations of each of the detergent compositions of 5 gm/liter of the
respective detergent compositions.
I ~ After each detergent composition is used in twelve wash eycles in a
washing machine the amount of encrustation or scaling that results, i.e., the
percent ash deposit is measured. The percent ash deposit measurement is
~; 30 determined by c~lcination of ~vashed swatches.
,,
29 - ;
'~ :
.
: .: `
` -- \
~IL3~5~
The results that are obtained are that the sodium hexametaphosphate
detergent composition's cleaning performance is equivalent or b~tter than the
sodium tripolyphosphate and the sodium hexametaphosphate detergent
composition provides improved anti-encrustation or anti-scaling performance
to that of the sodium tripolyphosphate.
As far as the encrustation buildup i6 concerned, no buildup is observed
with the hexametaphosphate, whereas a 6mal1 buildup i8 observed with the
sodium tripolyphosphste detergent builder salt.
The hexametaphosphate detergent builder s~lts can ~lso be used to
replace the polyphosphate builder salts in concentrated aqueous detergent
compositions. At concentrations of 50 to 6096, due ~o the
hexametaphosphate'6 polymeric structure, a viscous solution is obtained.
Because of the viscous nature of the concentrated aqueous solution the
physical stability and rheological behavior of the nqueous concentrated
composition is improved~
It is understood that the ~oregoing detailed description i6 given merely
by way of illustration and that variations may ~e made therein without
¦ depsrting irom e spirit of the iDvention.
1~ ~
¦~ 3D
. ~
