Note: Descriptions are shown in the official language in which they were submitted.
~ack~round of the Invention
(I) F;eld of Invention
This invention relates to stabilization of non-aqueous liquid
suspensions, especially non-aqueous liquid fabric-treating compositions.
More particularLy, this invention relates to non-aqueous liquid laundry
deterBent compositions which are made stable against phase separation under
~¦ both static and dynamic conditions and are easily pourable, to the method of
preparing these compositions and to the use of these compositions for
¦ cleaning soiled fabrics.
(2) Discussion of Prior Art
Liquid nonaqueous hea~y duty laundry deter8ent compositions are
well known in the art. For instance, compositions of this type may comprise
a liquid nonionic surfactant in which are dispersed particles of a builder,
I¦ as shown for instance in U.S. Patents No. 4,316,812; 3,630,929; 4,264,466;
I and 4,661,280.
I Liquid detergents are often considered to be more convenient to
, employ than dry powdered or particulate products and, thereEore, have found
substantial favor with consumers. They are readily measurable, speedily
dissolved in the wash water, capable of being easily applied in concentrated
solution~ or dispersions to soiled areas on garments to be laundered and are
non-dusting, and they usually occupy iess storage space. Additionally, the
liquid detergents may ha~e incorporated in their formulations materials
which can not stand drying operations without deterioration, wh~ch
materials are often desirably employed in the manufacture of particulate
detergent products.
`J
ZO~i304
~ lthough they are possessed of many advantages over unitary or
particulate solid products, liquid detergents often have certain inherent
disadvantages too, which have to be overcome to produce acceptable
co~mercial 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 chanees and it becomes either too thick
to pour or so thin as to appear watery. Some clear products become cloudy
and others gell on standing.
The present inventors have been extensively involved 8S part of an
overall corporate research effort in studying the rheological behavior of
nonionic liquid surfactant systems with particulate matter suspended
therein. Of particular interest have been non-aqueous, built, liquid
laundry detergent compositions and the problems of phase separation and
settling of the suspended builder and other laundry additives. These
considerations have an impact on, for example, product pourability,
dispersibility and stability.
It is known that one of the major problems with built, liquid
laundry detergents is their physical stability. This problem stems from the
fact that the density of the solid quspended particles is higher than the
density of the liquid matrix. Therefore, the particles tend to sediment
according to stoke's law. Two basic solutions exist to solve tbe
sedimentation problem: increasing liquid matrix vlscosity and¦or red~cing
solid particle size.
For instance, it is known that such suspensions can be stabilized
against settling by adding inorganic or organic thickening agents or
dispe:sants such as, for example, very hiBh sorEace area inorhanic
;Z~15309~
materials, e.g. finely divided silica, clays etc., organic thickeners, such
as the cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes,
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 performance of the formulation. U.S. Patent
i 4,661,280 to T. Ouhadi, et al, discloses the use of aluminum stearate for
increasing stability of suspensions of builder salts in liquid nonionic
surfactant. The addition of small amounts of aluminum stearate increases
yield stress without increasing plastic viscosity.
, According to U.S. Patent 3,985,668 to W. L. Hartman, an aqueous
false body fluid abrasive ~couring composition is prepared from an aqueous
liquid and an appropriate colloid-forming materials, such as clay or other
inorganic or or~anir thickening or suspending agent, especially smectite
, clays, and~a relatively light, water-insoluble particulate filler material,
which, like the abrasive materials, is suspended throughout the false body
fluid phase. The lighweight filler has particle size diameters ranging
from 1 to 250 microns and a specific gravity less than that of the false
body fluid phase. It is suggested by Hartman that inclusion of the
relatively light, insoluble filler in the false body fluid phase helps to
minimize phase separation, i.e. minimize for~ation of a clear liquid layer
l above the false body abrasive composition, first, by virtue oE its buoyancy
! exerting an upward force on the structure of the colloid-forming aBent in
I the false body phase counteracting the tendency of the heavy abrasive to
¦ compress the false body structure and squeeze out liquid. Second, the
Eill r material acts as a bulting ag~nt replacing a portion of the =ater
'J
2'~153(~
wllich would normally be used in the absence of the filler material, thereby
resulting in less aqueous liquid available to cause clear layer formation
and separation.
British Application GB 2,168,377A, p~lblished June 18, 1986,
discloses aqueous liquid dishwashing detergent compositions with abrasive,
colloidal clay thickener and low density particulate filler having particle
! sizes ranging from about 1 to about 250 microns and densities ranging from
about 0.01 to about 0.5 g/cc, used at a level of from about 0.077. to about
l 1% by weight of the composition. It is suggested that the filler material
'¦ improves stability by lowering the specific graYity of the clay mass so thati! it floats in the liquid phase of the composition. The type and amount of
filler is selected such that the specific gravity of the final composition
i is adjusted to match that of the clear fluid (i.e. the compositon without
clay or abrasive materials).
I It is also known to include an inorganic insoluble thickeningagen~ or dispersant of very high surface area such as finely divlded silica
of extremely fine particle slze (e.g. of 5-100 millimicrons diamcter such as
sold under the name Aerosil) or the other highly voluminous inorganic
carrier materials as disclosed in U.S. Patent 3,630,929.
It has long been known that aqueous swelling colloidal clays, such
as bentonite and montmorillonite clays, can be modified by exchange of the
metallic cation groups with organic groups, thereby changing the hydrophilic
clays to organophilic clays. The use of such organophilic clays as gel-
forming clays has been described in U.S. Patent 2,531,427 to ~.A. ~auser.
Improvements and modifications of the organophilic gel-forming clays are
, escribed, for ~xa p1~, in the io11Owing U.S. Patents: Z,9,6,506 - Jordan
4,105,578 - Finlayson, et al.; 4,208,218 - Fin1ayson; 4,287,086 - Finlayson;
4,434,075 - Mardis, et al.; 4,434,076 - Mardis, et al.; all assigned to NL
I~dustries, Inc., formerly National Lead Company. Accordlng to these NL
patents, these organophilic clay gellants are useful in lubricating
greases, oil based muds, oil base packer fluids, paints, paint-varnish-
lacquer removers, adhesives, sealants, inks, polyester gel coats and the
like, However, use as a stabilizer in a non-aqueous liquid detergent
I composition for laundering fabrics has not been suggested.
On the other hand, the use of clays in combination with quaternary
ammonium compounds (often referred to as "QA" compounds) to impart fabric
¦¦ softening benefits to laundering compositions has been described. Yor
instance, mention can be made of the British Patent Application GB 2,141,152
A, published December 12, 1984, to P. Ramachandran, and the ~any patents
referred to therein for fabric softening compositions based on organophilic
QA clays. ~
l According to the aforementioned U.S. Patent 4,264,466 to Carleton,
I et al., the physical stability of a dispersion of the particulats materials,
! such as detergent builders, in a non-aquoeus liquid phase is improved byusing as a primary suspending agent an impalpable chain structure type clay,
including sepiolite, attapulgite, and palygorskite clays. The patentees
state the comparative examples in this patent show that other types of
clays, such as montmorillonite clay, e.g. Bentolite L. hectorite clay (e.~.
Veegum T) and kaolinite clay (e.g. Hydrite PX), even when used in
conjunction with an auxiliary suspension aid, including cationic
surfactants, inclusive of QA compounds, are only poor suspending agents.
Carleton, et al. also refer to use of other clays as suspension aids and
, ..
6 ;-
m~n~ion, as e~amples, U.S. Patents 4,049,034 and 4,005,027 (hoth aqueous
systems); and U.S. Patents 4,166,G39; 3~259J574; 3,557,037 and 3,549,542;
and U.K. ratent Application 2,017,072.
Con~only assigned copending application Serial No. 063,199, filed
June 12, lg87 (Atty's Docket IR-347LG) discloses incorporation into non- ;
! aqueous liquid fabric treating compositions of up to about lZ by weight of
l an organophilic water-swellable s~ectite clay modified with a cationic
I nitrogen-containing compound including at least one long chain hydrocarbon
having from about 8 to about 22 carbon atoms to form an elastic network or
structure throughout the suspension to increase the yield stress and
increase stability of the suspension.
! While the addition of the organophilic clay improves stability of
i the suspension, still further improvements are desired especially for
particulate suspensions having relatively low yield values for optimizing
dispensing-and dispersion during use.
I Grinding to reduce the particle size as a means to increase
product stability provides the following advantages:
(1) the particle specific surface area is increased, and,
therefore, particle wetting by the non-aqueous vehicle (liquid non-ionic) is
proportionately improved; and
(2) the average distance between pigment particles is reduced
! with a proportionate increase in particle-to-particle interaction.
Each of these effects contributes to increase the rest-gel
! strength and the suspension yield stress while at the same time grinding
,¦ significantly reduces plastic viscosity.
!~ The above-mentioned U.S. Patent 4,316,~12 discloses the benefits
! f grinding solid particles e g builder and bleach to an a~erage
~0153~
particle ~iameter oE less than 10 microns. However, it has been found that
merely grinding to such small particle sizes does not, by itselt, impart
sufficient long term stability against phase separation.
In the commonly assigned copending application filed on July 15,
1987 in the names of N. Dixit, et al. under Serial No. 073,653 (Attorney's
Docket I.R.-4494), and titled "STABLE NON-AQUEOUS CLEANING COMPOSITION
CONT~INING LOW DENSITY FITTFR AND METHOD OF USE" the use of low density
i filler material for stabilizing suspensions of finely divided solid
I particulate matter in a liquid phase against phase separation by equalizing
! the densities of the dispersed particle phase and the liquid phase isl disclosed. These modified liquid suspensions exhibit e~cellent phase
I stabilization when left to stand for extended periods of time, e.g., up to
6 months or longer or even when subjected to moderate shaking. ~owever, it
has recently been observed that when the low-density filler modified
suspensions are subjected to strong vibrations, such as may be encountered
durlng transportation by rail, truck, etc. 9 the homogeneity of the
dispersion is degraded as a portion of the low density filler migrat~s to
the upper surface of the liquid suspen~ion.
In co~monly assigned, copending application Serial No. 073,551
filed July 15, 1987 in the name of Cao et al. IAttorney's Docket IR 344LG)
entitled "Stable Non-Aqueous Suspension Containing Organophilic Clay And
Low Density Filler" the use of the low density filler ~aterial for
stabilizing suspensions of finely divided solid particulate matter in
liquid phase against phase separation is disclosed as being improved by the
incorporation of organophilic modified clays which aid in resisting the
destabilizing effect of strong vibrations.
v
Z~
Nonetheless, still further improvements are desired in the
stability of non-aqueous liquid fabric treating compositions.
ln addition to the problem of se~tling or phase separation the
non-aqueous liquid laundry detergents based on liquid nonionic surfactants
suffer from the drawback that the nonionics tend to gell when added to cold
water. This is a particularly important problem in the ordinary use of
European household automatic washing machines where the user places thz
laundry deter8ent composition in a dispensing unit (e.g. a dispensing
drawer) of the machine. During the operation of the machine the deterBent
in the dispenser is subjected to a stream of cold water to transfer it to
the main body of wash solution. ~specially during the winter months when
the detergent composition and water fed to the dispenser are particularly
cold, the detergent viscosity increases markedly and a gel forms. As a
result some of the composition is not flushed completely off the dispenser
during operation of the machine, and a deposit of the composition builds up
with repeated wash cycles, eventually requiring the user to flush the
dispenser with hot water.
The gelling phenomenon can also be a pr~blem whenever it is
desired to carry out washing using cold water as may be recommended for
certain synthetic and delicate fabrics or fabrics which can shrink in warm
or hot water.
Partial solL.ions to the gelling problem in aqueous, substantially
builder-free compositions have been proposed and include, for e~ample,
diluting the liquid non-ionic with certain viscosity con~rolling solvents
and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (see
.S. Patent No. 3,953,380), alkali metal for:ates a~d ~di ates (see u~
Z~153~
Patent No. 4,363l147), hexylene glycol, polyethylene glycol, etc. and
nonionic structure modification and organization.
As an example of nonionic surfactant modification one particularly
successul result has been achieved by providing an acid group on the
nonionic. In this regard see U.S. Patent 4,749,512, the disclosure of which
is incorporated herein by reference.
In addition, these two patents each disclosed the USQ of up to at
most about 2.5Z of the lower alkyl (C~ - C4) etheric derivatives of the
lower (Cz - C3) polyols, e.g. ethylene glycol, in these aqueous liquid
builder-free dPtergents in place of a portion of the lower alkanol, e.g.
ethanol, as a viscosity control solvent. To similar effect are U.S.
Patent Nos. 4,111,855 and 4,201,686. However, there is no disclosure or
suggestions in any of these patents that these compounds, some of which are
commercially available under the tradename Cellosolve R , could function
eifectively as viscosity control and gel-pre~enting agents for non-aqueous
liquid nonionic surfactant compositions, especially such compositions
containing suspended builder salts, such as the polyphosphate compounds or
alkali metal citrate,and especially particularly such compositons which do
not depend on or require the lower alkanol solvents as viscosity control
agents .
Further~ore, British Patent Specification No. 1,600,981 mentlons
that in non-aqueous nonionic detergent compositions contaiuing builders
suspended therein with the aid of certain dispersants for the builder, such
as finely divided silica and/or polyether group containing compounds naving
molecular weights of at least 500, it may be advantageous to use mixtures
of nonionic surfactants, one of which fulfills a surfactant function and the
~ ..
,.
Z(~1~3C~
o~hcr ~E which boLh fulfills a surfactant function and reduces the pour
point of the compositions. ~he former is exemplified by C,z - C~s fatty
alcuhols with 5 to 15 moles of etylene and/or propylene oxide per mole.
~ he other surfactant is exemplified by linear C~ - C~ or branched
C~ - C,l fatty alcohols with 2 to 8 moles ethylene andlor propylene oxide
per mole. Again, there is no teaching that these low carbon chain
compounds could control the viscosity and prevent gelation of the heavy
duty non-aqueous liquid nonionic surfactant compositions with builder
suspended in the nonionic liquid surfactant.
.5ummary of the Invention
j Accordingly, it is an object of this invention to provide liquid
fabric treating compositions which are suspensions of insoluble fabric-
treating particles in a non-aqueous liquid and which are storage and
transportation stable, easily pourable and dispersible in cold, warm or hot
I water.
Another object of this invention is to formulate highly built
heavy duty non-aqueous liquid nonionic surfactant laundry detergent
! compositions which resist settling of the suspended solid particles or
separation of the liquid phase.
A still further objeet of this invention is to provide nonionic
liquids compositions which are readily dispersible in water, particularly
laundry bath water.
The Foregoing objects are achieved by providing a heterogenous
system of solids in a liquid medium which is structured to act as a solid
i during states of rest and under the ordinary stresses of vibrations,
oseillations, shear forces and the like thieh oeeur during the handling
Z~1~3~
(e.g. trallsportatioll e~c.) of the packaged product. When the structure is
broken or destroyed, the system acts as a conventional solids suspension ln
a liquid vehicle or matri~, i.e. it is flowable, pourable, and of course in
this state, ~tokes Law takes over and the solid suspended matter may settle
and the liquid solid phases stratify. It has been determined that several
, rheological parameters are meaningful indications ofthe stability of a
solids suspension in a liquid phase system. Some of these parameters are
storage modulus or loss modulus (G"), relaxation time, critical strain
(i.e. structure not destroyed below the strain), and structure recovery.
Targets to reach for optimi~ed stability are a long relaxation time (G'>G"),
a critical strain above 0.1 and a recovery time shorter than 1 minute.
i These and other objects of the invention which will become more
apparent hereinafter have been accomplished based on the inventors' I
discovery that by adding a relatively small amount of an amphiphilic
I carboxy-containing addition polymer. The polymers are derived from ~ ~ ~
i monethylenically unsaturated carboxy-containing monomers which also contain
at least one other chalcogen-containing group substituted with at least
one group of at least 2 carbon atoms.
The polymers may be homopolymers, copolymers, ter-polymers (i.e.
interpolymers) or block interpolymers (e.g. block copolymers)~
The polymers may vary in molecular weight from several (2, 3, 4
! etc.) hundred, preferably several thousand (2, 3, 4, 5 etc.) and more
preferably tens of thousands (e.g. 20,000, 30,000, 50,000, 70,000) to
several million ~2, 3J 8, 10 etc.). The most highly preferred r 8 ges will
I depend somewhat on the particularly monomer moieties, but generally this
ill be ~bout MW = 75,000 to 750,000. The ~nount of poly=~r in the
.
~!~153~)4
composition may v~ry from about 0.01% to about 10% by weight, and preferably
from about 0.05% to about 5% by weight. Typical amounts are O.lO; 0.20
and 0.25.
The polymer, in addition to the carboxy group contains (preferably
in the same monomer moiety) a further chaleogen group, i.e. oxygen, nitrogen
i or sulfur, which is substituted by a grouping of at least 2 carbon atoms.
Illustrative groups are carboxy, carboxamido, sulfonate, etc. Specific
groups include carboethoxy, carbobutoxy, N-ethyl carboxamido, N,N-diethyl
carboxamido, N-n-butyl-carboxamido, etc.
Specific monomer moieties of particular advantage are the 0~ ~ ~
unsaturated dicarboxylic anhydride and especially those of the formula
~ . I ~,0
111 C~
wherein R1 and R2 are independently selected from the group consisting of
hydrogen, halogen, alkyl, aryl, aralkyl, (and substituted alkyl, aryl or
aralkyl), or --S03~.
~xample of these compounds are:
maleic anhydride
chloromaleic anhydride
citraconic anhydride (methylmalelc)
f = rlc anhydride
mesaconic anhydride
phenylmaleic anhydride
benzyl maleic anhydride
! sulfo~aleic anhydride
aconitic anhydride
~l itaconic anhydride
methylene malonic anhydride
alkyl succinic anhydride and the like
~20153~l4
It is preferred to provide the carboxy monomer moieties in
conjunction with other copolymerizableC~, ~ ethylenically unsalturated
monomers. These include:
vinyl ethers e.g.,
vinyl wethyl ether
vinyl ethyl ether
vinyl n-propyl ether
I vinyl iso-proply ether
vinyl n-butyl ether
vinyl iso-butyl ether
vinyl iso-octyl ether
l vinyl phenyl ether
I a-chlorovinyl phenyl ether
I vinyl B-naphthyl ether
! vinyl esters. e-8-.
l vinyl acetate
! vinyl propionate
vinyl butyrate
l v;nyl caproate
! vinyl stearate, etc.
vinyl halides, e.g.,
vinyl chloride
vinyl fluoride
vinyl bromide
acrylic acid and esters, e.g.,
~ methyl acrylate
i ethyl acrylate
propyl alcrylate
, acrylic acid derivatives, e.g.,
methacrylic acid and esters
a-hallGacrylic acid and esters
acrylonitrile
methacrylonltrile
acrylamide
methacrylamide
N-alkyl acrylamides
N-aryl acryla~ides
N-vinyl heterocycles, e.g.,
N-vinyl pyrrolidone
N-vinyl 3-morpholinones
N-vinyl oxazolidone
N-vinyl imidazole
styrene
I alkyl styrenes, e.g., a-methyi styrene
vinylidene chloride
l vinyl ketones, e.g., methyl vinyl ketone
i olefins such as
ethylene
14
.,
:.
-.
3~
p ropylené
i~sobutylene
butene-l
2,4,4-trimethyl pentene-l
hexene-l
3-methyl-b~tene-1, and the like.
The anhydride-ethylenically unsaturated interpolymers preferably
contain the two moieties in equimolar amount whereby the repeating unit in
the interpolymer contains 1 anhydride and 1 comonomer moiety. Other ratios
are feasible 3.t. 5:4, 4:5, 3:2, 2:3, 2:1, 1:2 etc.
Examples of speciiic interpolymers which may be employed are:
vinyl methyl ether-maleic anhydride
vinyl ethyl ether-maleic anhydride
i styrene-maleic anhydride
! a-methyl styrene-maleic anhydride
i ethylene-maleic anhydride
l vinyl methyl ether-citraconic anhydride
I vinyl methyl ether-itaconic anhydride
vinyl methyl ether-chlormaleic anhydride
vinyl chloride-maleic arlhydride
vinyl acetate-maleic anhydride
vinyl chloride-vinyl acetate-maleic anhydride
styrene-vinyl acetate-maleic anhydride
An especially useful type of polymer (Z) is one based on an ~ ,~
- ethylenically-unsaturated dicarboxylic acid or anhydride (e.g. maleic
anhydride) and a copolymerizable ~ ~ - ethylenically unsaturated comoner
(e.g. vinyl methylether, ethylene, styrene, N-vinyl pyrrolidone etc.). A
further particularly useful sub-group covers the mono esters (e.g. 1/2-
butyl, l/~-ethyl, 1/2-isohe~yl) of these polymers. Another useful subgroup
involves the cross-linked (or reaction products) of the interpolymers and
especially polymers of the Z type utilizing a dif~ctional reagent such as
a diol, di-theol or the like. Illustrative crosslinking atents are glycols
such as diethylene glycol, triethylene glycol, 1,6 hexanediol, polyethylene
I glycols with molecular weights ranging from several hundred (e.g. 200, 300,
.
, I
I i 15
,1
zn~
~lO0, etc.) to several hundred thousand (100,000; 150,000; 200,000; 250,000;
350,000; 500,00 etc.) and especially those in the range of about 400 to
about 40,000. Where such a cross linking agent is used, the amount thereof
may vary from 1% by weight based on the weight of the polymer to 10 times
I the weight of the polymer, preferably the ratio of polymer to cross-linker
i should range from about 10:1 to 1:5 and most preferably 5:1 to 1:2.
In the preferred embodiment of special interest herein the liquid
phase oE the composition of this invention is comprised predom mantly or
totally of liquid nonionic synthetic organic detergent. A portion of the
liquid phase may be composed, however, of organic solvents which may enter
the compos~tion as solvent, vehicles or carriers for one or more of the
solid particulate ingredients, such as in enzyme slurries, perfumes, and the
like. Also as will be described in detail below, or~anic solvents, such as
alcohols and ethers, may be added as further viscosity control and antl-
gellin~ ag-ents.
The nonionic synthetic organic detergents employed in tho practice
of the invention may be any of a wide variety of such compounds, which are
well known and, for example, are described at length in the text Surface
Active ARents, Vol. II, by Schwartz, Perry and Berch, published in lg58 by
Interscience Publishers, and in McCutcheon's Deter~ents and Emulsifiers,
1969 Annual, the rele~ant dlsclosures of which are horeby incorporated by
reference. Usually, the nonionic detergents are poly-lower alkoxylated
lipophiles wherein the desired hydrophile-lipophile balance is obtained
from addition of a hydrophilic poly-lower alkoxy group to a lipophilic
moiety. A preferred class of the nonionic detergent employed is the poly-
lower alkoxylated higher alkanol wherein the alkanol is of 10 to 22 carbon
- Z~
atoms and wherein the number of mols of lower alkylene oxide (of 2 or 3
carbon atoms) is from 3 to 20. Of such materials it is preferred to employ
those wherein the higher alkanol is a higher fatty alcohol of about 12 to 18
carbon atoms and which contain from 3 to 14, preferably 3 to 12 lower alkoxy
groups per mol. The lower alkoxy is often just ethoxy but in some
instances, it may be desirably mixed with propoxy, the latter, if present,
often being in a minor (less than 50% proportion). Exemplary of such
compounds are those wherein the alkanol is of 12 to 15 carbon atoms and
which contain about 7 ethylene oxide groups per mol, e.g., Neodol 25-7 and
Neodol 23-6.5, which products are made by Shell Chemical Company, Inc. The
i former is a condensation product of a mixture of higher fatty alcohols
I averaging about 12 to 15 carbon atoms, with about 7 mols of ethylene o~ide
and the latter is a corresponding mixture wherein the carbon atom Gontent
I 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 linesr secondary alcohol etho~ylates made
by Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15
carbon atoms linear secoodary 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 compositions 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, with the higher fatty alcohol being of 14 to 15 carbon atoms and
the number of ethylene oxide groups per mol beinR about 11. Such products
17
2()153~
are also made by Shell Chemical Company. Another preferred class of useful
nonionics are represented by the commercially well know class of nonionics
which are the reaction product of a higher linear alcohol and a mixture of
ethylene and propylene oxides, containing a mixed chain of ethylene oxide
and propylene oxide, terminated by a hydroxyl group. ~xamples include the
i nonionics sold under the Plurafac trademark of BASE, such as Plurafac RA309
i Plurafac RA40 (a C,3-CI, fatty alcohol condensed with 7 molPs propylene
I oxide and 4 moles ethylene oxide), Plurafac D25 (a C1,-C1l Eatty alcohol
, condensed with 5 moles propylene oxide and 10 moles ethylene o~ide),
¦ Plurafac B26, and Plurafac RA50 (a mixture of equal parts Plurafac D25 and
Plurafac RA40).
Generally, the mixed ethylene oxide-propylene oxide fatty alcohol
condensation products represented by the general formula
RO(C3H~jO)~(C2~1403q~H~
wherein R ls a straight or branched primary or secondary aliphatic
hydrocarbon, preferably alkyl or alkenyl, especially preferably aIkyl~ of
from 60 to 20, preferably 10 to 18, especlally preferably lZ to 18 carbon
atoms, p is a numblsr of up to 14, preferably 3 to 8, and q ls a number of up
to 14, preferably 3 to 12, can be advantageously used where low foamlng
characteristics are desired. In addition, these surfactants have the
advantage of low gelling temperatures.
Another group of liquid nonionics are available from Shell
Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 is an
ethoxylated C~-Cl, fatty alcohol with an average of 5 moles ethylene oxide;
~obanol 25-7 is an ethoxylated Cl2-Cl, fatty alcohol with an average of 7
moles ethylene ~xide; etc.
..
18
2n~s3~
Ill 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 407. to 1~0% of the number of carbon atoms in
the higher alcohol, such as ~0 to 60% thereof and the nonionic detergent
i will often contain at least 50% of such preferred poly-lower alkoxy higher
alkanol.
Higher molecular weight alkanols and various other normally solid
l 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 alkoxy chain, if
such branched alkyl is not more than three carbons in length. Normally, the
proportion of carbon atoms in such a branched configuration will be minor
rarely exceeding 20~ of the total carbon atom content of the alkyl.
Similarly although linear alkyls which are terminally joined to the alkylene
oxide chains are highly preferred and are cDnsidered to result in the best
combination of detergency, biodegradability and non-gelling characteristics,
medial or secondary joinder to the alkylene oxide in the chain may occur.
It is usually in only a minor proportion of such alkyls, generally less than
i 207. but, as is the case of the mentioned Tergitols, may be greater. Also,
when propylene oxide is present in the lower alkylene oxide cha~n, it will
usually be less than 20~ thereof and preferably less than lOZ thereof.
,;
z~
When greater proportions of non-terminally alkoxylated alkanols,
propylene oxide-containing poly-lower alkoxylated alkanols and less
hydrophile-lipophile balanced nonionic detergent than mentioned above are
employed and when other nonionic deter~ents are used instead of the
preferred nonionics recited herein, the product resulting mav not have as
good detergency, stability, viscosity and non-gelling properties as the
preferred compositions but use of viscosity and gel controlling compounds
can also improve the properties of the detergents based on such nonionics.
In some 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-gelllng and of desired viscosity. Also, it has been found that it is
only rarely necessary to utilize the higher molecular weight monionics for
their detergent properties since the preferred nonionics described herein
are excellent deter~ents and additionally, permit the atainment of the
desired viscosity ir- the liquid detergent without gelation at low
temperatures. Mixtures of two or more of tnese liquid nonionic~ can also be
used and in some case~ advantages can be obtain$d by the use of such
mixtures.
In view of their low gelling temperatures and low pour points,
another preferred class of nonionic surfactants includes the Cl~-CI~
secondary fatty alcohols with relatively narrow contents of ethylene oxide
in the range of from about 7 to 9 moles, especially about 8 moles ethylene
oxide per molecule and the Cg-C,L, especially C,O fatty zlcohols
ethoxylated with about 6 moles ethylene oxide.
~0~53(~4
Furthermore, in the compositions of this invention, it may be
advantageous to include an organic solvent or diluent which can function as
a viscosity control and gel-inhibiting agent for the liquid nonionic
surface active agents. Lower (C~-C6) aliphatic alcohols and glycols, such
as ethonol, isoprnpanol, ethylene glycol, hexylene glycol and the like have
been used for this purpose. Polyethylene glycols, such as P~G 400, are also
useful diluients. Alkylene glycol ethers, such as the compounds sold under
the trademarks, Carbopol and Carbitol which have relatively short
hydrocarbon chain lengths (C2-C~) and a low content of ethylene oxide (about
2 to 6 EO units per molecule) are especially useful viscosity control and
anti-gelling solvents in the compositions of this invention. This use of
the alkylene glycol athers is disclosed in U.S. Patent No. 4,753,750 filed
December 31, 19849 to T. Ouhadi, et al. the disclosure of which is
incorporated herein by reference. Suitable glycol ethers can be represented
by the following general formula
RO(CH2CH20),~E~
where R is a C2-C8, preferably Cz-C~ alkyl group, and n is a number of from
about 1 to 6, preferably 1 to 4, on average.
Specific examples of suitable solvents include ethylene glycol
monoethyl ether (C2EI~-O-CH2CLzOEl), diethylene ~lycol monobutyl ether (C~H9-
O-(CH~CII20)~H), tetraethylene glycol monooctyl ether (C~al7-O-(CL2CG20)~H),
etc. Diethylene glycol monobutyl ether i~ especially preferred.
Another useful antigelling agent which can be islcluded as a minor
component of the liquid phase, is an aliphatic linear or aliphatic
monocyclic dicarboxylic acid, such as the C~ to Cl2 alkyl and alkenyl
erivatives oE succinic acid or ~aleic acid, anl the corr~sponding
2~3~53~
anhydrides or an aliphatic monocyclic dicarboxylic acid compound. The use
of these compounds as antigelling agents in non-aqueous liquid heavy dut.y
built laundry detergent compositions is disclosed in U.S. Patent No.
4,744,916 to ~dams ~ Prossin filed July 18, 1985, the disclosure of which
is incorporated herein in its entirety by reference thereto.
Brief~y, these gel-inhibiting compounds are aliphatic linear or
aliphatic monocyclic dicarboxylic acid compounds. The aliphatic portion of
the molecule may be saturated or ethylenically unsaturated and the aliphatic
linear portion may be straight of branched. ~le aliphatic monocylic
i molecules may be saturated or may include a single double bond in the ring.
Furthermore, the aliphatic hydrocarbon ring may have 5- or 6-carbon atoms in
the ring, i.e. cyclopentyl, cyclopentenyl, cyclohexyl, or cyclohexenyl, with
one carboxyl group bonded directly to a carbon atom in the ring and the
other carboxyl group bonded to the ring through a linear aIkyl or alkenyl
group.
The aliphatic linear dicarboxylic acids have at least about 6
carbon atoms in the aliphatic moiety and may be alkyl or alkenyl having up
to about 14 carbon atoms, with a preferred range being from about ~ to 13
carbon atoms, especially preferably 9 to 12 carbon atoms. One of the
carboxylic acid groups (-COOFI) is preferably bonded to the terminal (alpha)
carbon atom of the aliphatic chain and the other carboxyl group is
preferably bonded to the next adjacent (beta) carbon atom or it may be
spaced two or three carbon atoms from the -position, i.e. on the y or
carbon atoms. The preferred aliphatic dicarboxylic acids are the
dicarboxylic acids and the corresponding anhydrides, and especially
preferred are derivatives of succinic acid of maleic acid and have the
! general formula:
s;~ l
R'-C-C-~ R'-C-C //
¦l ~ OH or (~)T.-C-C
wherein R' is an alkyl or alkenyl group of from about 6 to 12 carbon atoms,
preferably 7 to ll carbon atoms, especially preferably 8 to 10 carbon atoms,
i wherein ~=l, when --- is a double bond and ~=2, when --- is a single bond.
The alkyl or alkenyl group may be straight or branched. The
straight chain alkenyl ~roups are especially preferred. It ls not necessary
that R' represent a single alkyl or alkenyl group and ~lxtures of different
carbon chain lengths may be present depending on the starting materials for
preparing the dicarboxylic acid.
The aliphatic monocyclic dicarboxylic acid may be either 5- or 6-
membered carbon rings with one or two linear aliphatic groups bonded to ring
carbon atoms. The linear aliphatic groups should have at least about 6,
preferably at least about 8, especially preferably at least about 10 carbon
atoms, in total, and up to about 22, preferably up to about 18, especislly
preferably up to about 15 carbon atoms. When two aliphatic carbon atoms are
present attached to the aliphatic ring they are preferably located para~ to
each other. Thus, the preferred aliphatic cyclic dicarboxylic acid
compounds may be represented by the following structural for~ula
/T~
R'- C - RZ-COOH
~C-~COOH
where -T- represents -CH2 , -CHz=, -CH~-CH2- or -CH=C~-;
Rz represents an alkyl or alkenyl group of from 3 to 12 carbon
at~ms; ~nd
,i I
i3~
R, represents a hydrogen atom or an alkyl or alkenyl group of from
1 to 12 carbon atoms,
with the proviso that the total number of carbon atoms in RZ and
R ' is from about 6 to about 22.
Preferably -T- represents -CH2~CH2- or -CH-CH-, especially
preferably -CH=CH-.
R2 and RJ are each preferably alkyl groups of from about 3 to
about 10 carbon atoms, especially from about 4 to about 9 carbon atoms, with
the total number of carbon atoms in R and R3 being from about 8 to about
15. The alkyl or alkenyl groups may be straight of branched but are
preferably straight chains.
The amount of the nonionic surfactant is generally within the
range of from about 20 to about 70%, such as about 22 to 60% for example
25%, 307, 357. or 40Z by weight of the composition. The amount of solvent or
diluent when present is usually up to 207, preferably up to 15~, Eor
example, 0.5 to 15%, preferably 5.0 to 12%. The wciKht ratlo of nonionic
surfactant to alkylene glycol ether as the viscosity control and anti-
gelling agent, when the latter is present, is in the range of from about
100:1 to 1:1, preferably from about 50:1 to about 2:1, such as 10:1, 8:1,
6:1, 4:1 or 3:1. Accordingly, the continuous non-aqueous liquid phase may
comprise from about 30Z to about 70% by weight of the composition,
preferably from about 507. to about 607.
The amount of the dicarboxylic acid gel-inhibiting compound, when
used, will be dependent on such factors as the nature of the liquid nonionic
surfactant, e.g. its gelling temperature, the nature of the dicarbo~ylic
acid, other ingredients in the composition which might influence gellLng
24
~1153Q4
t:emperature, and the intended use (e.g. with hot or cold water,
geo~raphical climate, and so on). Generally, it is possible to lower the
gelling temperature to no higher than about 3C, preferably no higher than
about 0 C, with amount of dicarboxylic acid anti-~elling agent in the range
of about 1% to about 30~, pr~ferably from about 1.5% to about 15%t by
weight, based on the weight of the liquid nonionic surfactant, although in
any particular case the optimum amount can be readily determined by routine
experimentation~
The invention detergent compositions in the preferred embodiment
also include as an essential ingredient water-soluble and/or water-
dispersible detergent builder salts. Typical suitable builders include, for
example, those disclosed in the aforementioned U.S. Patents 4,316,81Z,
4,204,466, 3,630,929, and many others. Water-soluble inorganic alkaline
builder salts which can be used alone with the deterBent compound or in
admixture with other builders are alk~li metal carbonates, borates,
phosphates, polyphosphates, icarbonates, 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 hæxametaphosphate, sodium sesquicarbonate, sodium
mono and diorthophosphate, and potassium bicarbonate. Sodium
tripolyphosphate (TPP) is especially preferred where phosphate containing
ingredients are not prohibited due to environmental concerns. ~he alkali
metal silicates are useful builder salts which also function to make the
composition anticorrosi~e to washing machine parts. Sodium silicates of
NazO/SiO2 ratlos of from 1.6/1 to 1/3.2, especially about 1/2 to l/Z.8 are
preferred. Potassium silicates of the same ratios can also be used.
`~
Z~)153~9t
Another class of builders are the water-insoluble
aliminosilicates, both of the crystalline and amorphous type. Various
cystalline zeolites (i.e. aluminosilicates) are described in British Patent
],504,168, U.S. Patent 4,409,136 and Danadian Patents 1,072,835 and
! 1,087,477, all of which are hereby incorporated by reference Eor such
i descriptions. An example of amorphous zeolites useful herein can be found
in Belgium Patent 835,351 and this patent too is incorporated herein by
reference. The zeolites generally have the formula
(MzO)~ (AlzO~)y (SiOz)r W~zO
wherein n is 1, y is from 0.8 to 1.2 and preferably 1, is from 1.5 to 3.5
! or hi8her and preferably 2 to 3 and W is from 0 to 9, preferably 2.5 to 6
and M is preferably sodium. A typical zeolite is type A or similar
structure, with type 4A particularly preferred. The preferred
aluminosilicates have calcium ion exchange capacities of about 200
milliequival~nts per gram or greater, e.~. 400 meq/o g.
~ xamples of or~anic alkaline sequestrant builder salts which can
be used alone with the detergent or in admixture with other organic and
inorganlc builders are alkali metal, = onium or substituted ammonium,
aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetra-
acetate (EDTA), sodium and potassium nitrilotriacetates (NTA) and
triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates. Mi~ed salts of
these polycarboxylates are also suitable.
Other suitable builders of the organic type include
carboxymethylsuccinates, tartronates and glycollates and the polyacetal
carboxylates. The polyacetal carboxylates and their use in detergent
I compositions are described in 4,144,226; 4,315,092 and 4,146,494. Other
!
26
Z~)15~3V4
patents on similar builders include 4,141,676; 4,169,934; 4,201,858;
4,204,852; 4,224,420; 4,225,685; 4,226,96~; 4,233,422; 4,233,423; 4,302,564
and 4,303,777. Also relevant are European Patent Application Nos. 00150~4,
0021491 and 0063399. Particularly outstanding amoung the organic builders
are the non-nitrogeneous polycarboxylates such as citric acid, tartaric
I acid and the like. The preferred in this group are the sodium and potassium
citrates and tartrates and most preferred are the sodium citric acid salts,
especially the trisodium citrate, although the monosodium and disodium are
also good.
The porportion of the suspended detergent builder, based on the
total composition, is usually in the range of from about 30 to 70 weight
i percent, such as about 20 to 50 weight persent, for example about 40 to 50
weight percent of the composition.
According to the present invention, the physical stability of the
suspension of the detergent builder salt or salts or any other finely
divided suspended solid particulate additive, such as bleaching agent,
pigment, etc., in the liquid vehicle is drastically improved by thc presence
of small amounts of the amphiphilic polymer.
In preparing the compositions of the present invention, the
stabilizer, generally in a flaked or powdered form, is admixed with the
other solid ingredients and the liquid components, either in a conventional
mixing apparatus, such as a crutcher-type mixer, followed by transfer to a
milling apparatus or directly in a milling apparatus. In this latter case,
the mill rotor of an Attritor ball mill may be employed to mix the
I components. In a particularly preferred embodiment of the invention, the
stabilizer is first thoroughly mixed with the other solid ingredients, and
then this admixture of solid components is mixed with the liquid components.
Z'):153~
Since the compositions of this invention are generally highly
collcentrated, and, therefore, may be used at relatively low dosages, it is
often desirable to supplement the builder with an auxiliary builder such as
a polymeric carboxylic acid having high calcium binding capacity to inhibit
j incrustration which would otherwise be caused by formation of an insoluble
calcium phosphate, (e.g. where phosphate ion is present as from builder.
Such auxiliary builders are also well know in the art. For example,
mention can be made Sokolan CP5 which is a copolymer of about equal moles
of methacrylic acid and maleic anhydride, completely neutralized to form the
sodium salt thereof. l~e amount oi the auxiliary builder is generally up to
about 6 weight percent, preferably 1/4 to 4%, such as 1%, 2% or 3~, based on
the total weight of the composition.
In addition to the detergent builder, variou~s other detergent
additives or adjuvants may be present in the detergent pruduct to give it
additional desired properties, either of functional or aesthetic nature.
Thus, there may be included in the formulation, minor amount of soil
suspending or antiredeposition agents,e.g. polyvinyl alcohol, fatty amides,
sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose, usually in
amounts of up to lO weight percent, for example 0.1 to 10%, preferably 1 to
5%; optical brighteners, e.g. cotton, polyamide and polyester brighteners,
for example, stilbene, triazole and benzidone sulfone compositions,
especially sulfonated substituted triazinyl stilbene, sulfonated
naphthotriazole stilbene benzidine sulfone, et., most preferred are
stilbene and triazole combinations. Typically, amount of the optical
brightener up to about 2 weight percent, preferably up to 1 weight percent,
such as 0.1 to 0.~ weight percent, can be used.
.
z~s~
Bluing agents such as utramarine blue; enzymes, preferable
prot lytic er-zymes, such as subtilisin, bormelin, papain, trypain and
pensi:l, as well as amylasetype enzy~es, lipase type enzymes, and mixtures
thereof; bactericides, e.g. tetrachlorosalicylanilide, hexachlorophene;
fungicides; dyes; pigments (water dispersible); preservatives; ultraviolet
absorbers; anti-yellowing agents, such as sodium carboxymethyl cellulose,
complex of Cl2 to C~ alkyl alcohol with Cl2 to C~R alkylsulfate; p~
modifiers and pH buffers; color safe bleaches9 perfume, and anti-foam agents
or suds-suppressor, e.g. silicon compounds can also be sued.
The bleaching agents are classified broadly for convenience, as
chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by
sodium hypochlorite (NaOCl), potassium dichloroiosocyanuate (59% available
chlorine), and tricholorisocyanuric acid (95% available chlorine). Oxygen
bleaches are preferred and are represented ~y percompounds which liberate
hydrogen peroxide in solution. Preferred examples include sodiu~ and
potassium perborates, percarbones, and perpho3phate, and potassium
monopersulfate. Th~ perborates, partlcularly sodium purborate monohydrate,
are especially pref~rred.
The peroxygen compound is preferably used in admixture with an
activator therefor. Cuitable activators which can lower the effective
operating temperature of the peroxide bleaching agent are disclosed, for
example, in U.S. Patent 4,264,466 or in column 1 of U.S. Patent 4r4~0~244
the relevant disclosures of which are incorporated herein by reference.
Polyacylated compounds are preferred activators; among these, compounds such
as tetraacetyl ethylene diamine ("TAED") and pentaacetyl glucose are
particularly preferred.
~s~
Other useful activators include, for example, acetylsalicylic acid
derivatives, ethylidene benzoate acetate and its salt~, ethylidene
oarboxylate acetate and its salts, alkyl and alkenyl succinic anhydride,
tetraacetylglycouril t"TAGU"), and the derivatives of these. Other useful
classes of activators are disclosed, for example, in U.S. Patents 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 reaction between such peroxyacid and hydrogen peroxide in the wash
solution in the presence of metal ions. Preferred sequestering agents are
able to form a complex with Cu2+ ions, such that the stability constant (pk)
of the complexation is equal to or greater than 6, 25C, in water, of an
ionic strength of 0.1 mole/liter, pK being conventionally defined by the
formula: p~ = -log K where K represents the equilibrium constant. Thus, for
example, the pK values for complexation of copper ion with NTA and EDTA at
the stated conditions are 12.7 and 18.8, respectively. Suitable
sequestering agents include, for example, in addition to those mentioned
above, the compounds sold under the Dequest trademark, such as, for example,
diethylene triamine pentaacetic acid (DETPA); diethylene triamine
pentamethylene phosphoric acid (DTPMP); and ethylene diamine tetramethylene
phosphoric acid (EDITEMPA).
In order to avoid loss of peroxide bleaching, 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
~,
~;: ,; ,
20153(~ !
of the peroxide bleaching agent. Suitable inhibitor compounds are
disclosed in U.S. Patent 3,606,990, the relevant disclosure oE which is
incorporated herein by reference.
Of special interest as the inhibitor compound, mention can be made
of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In
the preferred nonaqueous compositions of this invention, s~itable amounts of
the hydro~ylamine salt inhibitors can be as low as about 0.01 to 0.4%.
Generally, however, suitable amounts of enzyme inhibitors are up to about
15%, for example, 0.1 to 10%, by weight of the composition.
Another useful stabilizer for use where desired in conjunction
with the polymer stabilizer, is an acidic organic phosphorus compound having
an acidic-POH group, as dislcosed ln the commonly assigned copending
application Serial No. 781,1A9, filed September 25, 1985, to ~roze, et al.,
acidic or~anic phosphorus compound, may be, for instance, a partial ester of
phosphoric acid and an alcohol, such as an alkanol having a lipophilic
character, having, for instance, more than S carbon atoms, e.g. 8 to 20
carbon atoms. A specific example is a partial ester of phosphoric acid and
a Clh to Cl~ alkanol. Empiphos 5632 from Marchon is made up of about 35%
monoester and 65% diester. When used amounts of the phosphoric acid
compound up to about 3%, preferably up to 1%, are sufficient.
As disclosed in U.S. Patent 4,749,51~., to Broze, et al., the
disclosure of which is incorporated herein by reference, a nonionlc
surfactant which has been modified to convert a free hydroxyl group to a
moiety having a free carboxyl group, such as a partial ester of a nonionic
surfactant and a polycarboxylic acid, can be incorporated into the
=mposition to turtùer improve rheo1Ogio=1 prop~rti=s. Por instance,
2'~153V~
amounts of the a~id-terminated nonionic surfactant of up to 1 per part of
the nonionic surfactant, such as 0.1 to 0.8 part, are sufficient.
Suitab]e ranges of these optional detergent additives are:
enzymes - 0 to 2~, especially 0.1 to 1.3~; corrosion inhibitors - about 0 to
40~, and preferably 5 to 30%; anti-foam agents and suds-suppressor - O to
15~, preferably 0 to 5~, for example 0.1 to 3~; thickening agent and
dispersants - 0 to 15%, for example 0.1 to 10~, preferably 1 to 5%; soil
suspending or anti-redeposition agents and anti-yellowing agents - 0 to 10%,
I preferably 0.5 to 5~; colorants, perfumes, brighteners and bluing agents
i total weight 0~ to about 2% and preferably 0~ to about 1~; pH modifiers
and pH buffers - 0 to 5%, preferably 0 to 2~; bleaching agent - 0 to about
40% and preferably OZ to about 25~, for example 2 to 20%; bleach stabilizers
and bleach activators 0 to about 15%, preferably 0 to 10%, for example,
0.1 to 8%; enzyme-inhibitors 0 to 15%, for example, 0.01 to 15~, preferably
0.1 to 10%;- sequestering agent of high co~plexing power, in the range of
up to about 5%, preferably 1/4 to 3%, such as about 1/2 to 2~. In the
selections of the adjuvants, they will be chosen to be compatible with the
main constitusnts of the detergent composition.
In a preferred form of the invention, the mixture of liquid
nonionic surfactant and solid ingredients is subjected to grinding, for
example, by a san mill or ball mill. Especially useful are the attrition
types of ~ill, such as those sold by Wiener-Amsterdam or Netzsch-Germany,
for example, in which the particle sizes of the solid ingredients are
i reduced to about 1-10 microns, e.g. to an average particle size of 4 to
5 microns or even lower (e.g. 1 micron). Preferably less than about 10%,
sspecially less than about 5 of all the suspended particles have particle
~)15;30~
sizes greater than 15 microns, preferably 10 microns. In view of increasing
costs in energy consumption as particle size decreases it is often preferred
that the average particle size be at least 3 microns, especially about 4
microns. Other types of grinding mills, such as toothmill, peg mil] and the
, like, may also be used.
i 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 are in contact with each other and are not
substantially shielded from one another by the nonionic suractant liquid.
! Mills which employ grinding balls. (ball mills) or similar mobile grindin8
elements have given very good results. Thus, one may use a laboratory batch
I attritor having 8 mm diameter steatite grinding balls. For larger scale
work a continuously operating mill in which there are 1 mm of l.5 ~m
dia~eter grinding balls working in a very small gap between a stator and a
rotor operating at a relatively high speed (e.g. a Co~all mill) may be
employed; when using such a mill, it is desirable to pass the blend of
nonionic surfactant and sollds first through a mill which does not effect
such fine grinding (e.g. a colloid mill) to reduce the particle size to less
than 100 microns (e.g. to sbout 40 microns) prior to the step of grinding to
an average particle diameter below about 18 or 15 microns ln the continuous
ball mill.
Alternatively, the powdery solid particles may be finely ground to
the desired size before blending with the liquid matrix, for instan~e, in a
~et-mill.
It is understood that the foregoing detailed deYcription is given
merely by way of illustration and that variation may be made therein
without departing from the spirit of the invention.
53~
It sh~uld also be understood that as used in the specification and
in the appended claims the term "non-aqueous" means absence of water,
however, small amounts of water, for example up to about 5~, preferably up
to about 2%, may be tolerated in the compositions and, therefore, "non-
aqueous" compositions can include such small amounts of water, whether added
l directly or as a carrier or solvent for one of the other ingredients in the
I composition.
The liquid fabric treating compositions of this invention may be
packa~ed in conventional ~lass or plastic vessels and also in single use
packages, such as the doserrettes and disposable sachet dispensers disclosed
I in commonly assigned copending application Serial No. 063,199, filed
June 12, 1987 (Attorney's Docket IR-347LG), the disclosure of which is
i incorporated herein by reference thereto.
The invention will now be described by way of the following non-
limitihg ex~mples in which all proportions and percentages are by weight,
unless otherwise indicate. Also, atmospheric pressure is used unless
otherwise indicated.
EKAMPI,E I
The following composition is prepared
% Wei~ht
C9-l1 fatty alcohol condensed with 5 moles of
ethylene oxide 46.95
Tri-enzymes A* 0.55
Perfume 0.50
Sodium Citrate-dehydrate 30.00
Tetra-acetyl ethylene diamine (TAED) 4.00
l Sodium perborate monohydrate 13.70
! Na maleate - metracrylate copolymer 2.0
E~hylene diamine tetra acetlc acid (EDTA)0.50
Sodium Carboxymethyl cellulose (CMC) 1.0
Titanium dioxide 0.40
>
53(~
~ptical brightener (Tinopol ArS-X) 0.30
Mono Butyl ester of poly (vinyl methyl ether/maleic acid) 0.lD
'SAVINASE 8.0 SL (NOVO) 36%
ALCALASE 2.5 SL (NO~O) 46
TERMAMYL 300 SL (NOVO) 18%
vinyl methyl ether/maleic anhydride
molar ration 1:1; M.W. 305,000
I The ioregoing composition has a pH = 9.5 when 5 g are dissolved in
i one liter of water ~0.5%).
The product is exceptionally stable with no separation or settling
of solids after more than 2 months.
EXAMPLE II
¦ Example I is repeated varyin~ the nonionic (and citrate content)
as follows
(A) 30% (citrate 47%)
(B) 40% (citrate 37Z)
(C) 52% (25Z citrate)
EXAMPLE III
Example I is repeated except that the nonionic is replaced by the
following in separate formulations in the percent indicated in the final
formulation
%
(A) Cl~ - Ct~ fatty alcohol condensed
with 7 moles of ethylene oxide and
then 4 moles of propylene oxide 46.95
(B) Gl, - C1, fatty alcohol condensed
with 4 moles of propylene oxide and
then 7 moles of ethylene oxide 46.95
! (c) A & B in 1:1 ratio 46.95
EXAMPLE IV
Examples I to III are each repeated in all parts using, first,
0.05% of the polymer ester, then 0.087, then 1.2%, then 1.5%.
L531~
EX~MPLE V
Each of the foregoing examples and all parts thereof is repeated
utilizing instead of the 1/2 butyl ester (MW 305,000), the following
A) 1/2 butyl ester MW 262,~00
, B) 1/2 b~tyl ester MW 550,000
I C) 1/2 N-propyl ester MW 305,0Q0
; D) 1/2 isohexyl ester MW 240,000
E) 1/2 isooctyl ester MW 305,000
F) 1/2 butyl estsr of vinyl ethyl
ester-maleic anhydride (1:1)
interpolymer MW 325~000
EXAMPLE VI
. Each example is a8ain repeated using hower as thE interpolymer the
. following
, A) 1/2 butyl ester of vinyl methyl
i ether-methyl maleic anhydride (1:1) MW 350,000
B) 1/2 butyl ester of vinyl methyl
ether-citriconic anhydrice (1:1) MW 420,000
C) 1/2 butyl ester of vinyl
pyrrol:idone-maleic anhydride (1:1) MW 300,000
D) 1/2 iso-octyl ester of vinyl
- pyrrolidone-maleic anhydride (1:1) MW 450,000
EXAMPL~ VII
Examples I, II, III~ IV are each repeated using in place oE thc
mono (i.e. 1/2)-buty:L ester polymer the following (at equal weight amounts)
A) mono butyl ester of ethylene
malelc anhydride interpolymer (1:1) MW 200,000
B) mono butyl ester of styrene
maleic anhydride interpolymer (1:1) MW 3'iO,000
C) mono butyl ester of vinyl acetate
maleic anhydride interpolymer (1:1) MW 305,000
D) mono ethyl ester of butyl acrylate
maleic anhydride interpolymer (1:1) MW 450,000
EXAMPLE VIII
The following composition is prepared
. ~ Wei~ht
il
" C~ - C " fatty alcohol condensed with 5 .
moles ethylene oxide 38.0
Z~1531U~
Sodium citrate dehydrate 27.8
Sodillm perborate monohydrate 14 5
TAF,D activator 3 7
Titanium dioxide 0 4
Optical brightener 0 3
EDTA 0.5
Trienzymes A 0.55
Perfu~e O.5
. Pluronic L42 Diol -
I Vinyl methyl ether-maleic anhydride
Polymer (~antrez AN 119) 0-0
Propylene carbonate 12.6
A prod,ct of e~eellent stability is obtained.
