Note: Descriptions are shown in the official language in which they were submitted.
~066008
Background of the Invention
Field of the Invention:
_ _
The present invention relates to non-aqueous, liquid,
heavy-duty laundry detergents. More particularly, this invention
relates to non-aqueous, liquid, heavy-duty laundry detergents
containing secondary ethoxylate nonionic surfactants of reduced
foaming tendency and the method of making such detergents.
Description of the Prior Art:
-
Liquid, non-aqueous, heavy-duty, laundry detergent
compositions are well-known in the art. For instance,
compositions of that type may comprise a liquid nonionic
surfactant in which are dispersed particles of a builder, as
shown for instance in U.S. Patents 4,316,812; 3,630,929;
4,264,466; and British Patents 1,205,711; 1,270,040 and
1,600,981.
Liquid detergents are often considered to be more
convenient to employ than dry powdered or particulate products
and, therefore, have found substantial favor 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 less storage space.
Additionally, the liquid detergents may have incorporated in
thelr formulations materials which could not stand drying
operations wi~thout deterioration, which materials are often
desirably employed in the manufacture of particulate detergent
products. Although they 3re possessed of many advantages over
unitary or particulate solid products, liquid detergents often
have certain inherent disadvantages too, which have to be
overcome to produce acceptable commercial detergent products.
20~0~8
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. Various
techniques have been utilized to overcome the aforementioned
problems. However, one continuing problem is that because of the
high level of surfactant in non-aqueous, heavy-duty, laundry
detergents, only low-foaming nonionics, e.g., linear alkyl
ethoxylate/propoxylate nonionics, are commonly used. Such linear
alkyl ethoxylate/propoxylate nonionics have certain dis~dvantagec
particularly with respect to cost and biodegradability.
Secondary alkyl ethoxylate nonionics would be an attractive
alternative to the linear alkyl ethoxylate/propoxylate,
particularly with respect to cost, performance and
biodegradability, except their foam levels are unacceptably high,
especially for European washing conditions.
Summary Of The Invention
Accordingly, it is an object of the present invention
to provide a non-aqueous, liquid, heavy-duty, laundry detergent
containing secondary alkyl ethoxylate nonionics with a low
foaming tendency.
It is a further object of the present invention to
provide a process of making a non-aqueous liquid, heavy-duty,
laundry detergent containing secondary alkyl ethoxylate nonionics
with a low foaming tendency.
These and other objects of the invention, as will
become apparent hereinafter, may be achieved, in one embodiment,
by the provision of a low-foam, non-aqueous, liquid, heavy-duty,
laundry detergent comprising a detersively effective amount of a
2 ~ 8
nonionic surfactant, said nonionic surfactant comprising a
~olyethoxylated secondary higher alkanol wherein said secondary
higher alkanol has 8 to 22 carbon atoms and the number of moles
of ethylene oxide is from 2 to 20 per mole of secondary higher
alkanol; a viscosity-controlling and anti-gelling effective
amount of a solvent selected from the group consisting of
monohydric alcohols, dihydric alcohols, alkylene glycols and
alkylene glycol ethers; an anti-gelling effective amount of a
diacid compound selected from the group consisting of aliphatic
linear dicarboxylic acids and aliphatic monocyclic dicarboxylic
acids; a detergent building effective amount of at least one
builder salt; an antifoaming effective amount of a colloidal
silica containing silicone composition.
In another embodiment, the present invention provides a
low-foam, non-aqueous, liquid, heavy-duty, laundry detergent
comprising a detersively effective amount of a nonionic
surfactant, said nonionic surfactant comprising a polyethoxylated
secondary higher alkanol wherein said secondary higher alkanol
has 8 to 22 carbon atoms and the number of moles of ethylene
oxide is from 2 to 20 per mole of secondary higher alkanol; a
viscosity-controlling and anti-gelling effective amount of a
solvent selected from the group consisting of monohydric
alcohols, dihydric alcohols, alkylene glycols and alkylene glycol
ethers; an anti-gelling effective amount of a diacid compound
selected from the group consisting of aliphatic linear
dicarboxylic acids and aliphatic monocyclic dicarboxylic acids; a
detergent building effective amount of at least one builder salt;
an antifoaming effective amount of a silicone composition free
of colloidal silica; prepared by the sequential steps of (a)
admixing said nonionic surfactant with said silicone composition,
2~60~8
(b) admixing the admixt~re of step (a) with said solvent, (c)
admixing the admixture of step (b) with said diacid compound, and
(d) admixing the admixture o step (c) with the remaining
ingredients.
In a further embodiment, the present invention provides
a method of making a low-foam, non-aqueous, liquid, heavy-duty
laundry detergent comprising a detersively effective amount of a
nonionic surfactant, said nonionic surfactant comprising a
polyethoxylated secondary higher alkanol wherein said secondary
higher alkanol has 8 to 22 carbon atoms and the number of moles
of ethylene oxide is from 2 to 20 per mole of secondary.higher
alkanol; a viscosity-controlling and anti-gelling effective
amount of a solvent selected from the group consisting of
monohydric alcohols, dihydric alcohols, a'kylene glycols and
alkylene glycol ethers; an ~nti-gelling effective amount of a
diacid compound selected from the group consisting of aliphatic
linear dicarboxylic acids and aliphatic monocyclic dicarboxylic
acids; a detergent building effective amount of at least one
builder salt; an antifoaming effective amount of a silicone
composition free of colloidal silica; said processing comprising
~: the steps of: (a) admixing said nonionic surfactant with said
silicone composition, (b) admixing said admixture of step (a)
~ with said solvent, (c) admixing said admixture of step (b) with
:~ said diacid compound, and (d) admixing said admixture of step (c)
~ 25 with the remaining ingredients.
:~ Detailed Description Of The Invention
The nonionic surface active agents useful in the
present invention are characterized by the presence of an organic
hydrophobic and an organic hydrophilic group and are typically
produced by the condensation of an organic aliphatic or alkyl
2~6~0~8
aromatic hydrophobic compound with ethylene oxide (which is
hydrophilic in nature). ?ractically any hydrophobic compound
havin~ a carboxy, hydroxy, amido or amino group with a Cree
hydrogen attached to the nitrogen can be condensed with ethylene
oxide or with the ~olyhydration product thereof, i.e.
~olyethylene glycol, to form a nonionic surfactant. The length
of the hydrophilic (polyoxyethylene) chain can be readily
adjusted to achieve the desired balance between the hydrophobic
and hydrophilic groups.
The nonionic surfactant employed is preferably a
polyethoxylated secondary hi~her alkanol wherein the se,condary
higher alkanol has 8 to 22 carbon atoms, preferably 9 to 18
carbon atoms, most preferably 11 to 15 carbon atoms; and wherein
the number of moles o~ ethylene oxide is from 2 to 20, preferably
lS 5 to 12, most preferably 7 to 9, per mole of the secondary higher
alcohol. Of such materials, it is preferred to employ those
wherein the secondary higher alkanol has 11 to 15 carbon atoms
and the number of moles of ethylene oxide is 7 and those wherein
the secondary higher alkanol has 11 to 15 carbon atoms and the
number of moles of ethylene oxide is 9. Especially preferred is
a 1:1 mixture of a polyethoxylated secondary higher alkanol
wherein the secondary alkanol has 11 to 15 carbon atoms and the
~number of moles of ethylene oxide is 7 and a polyethoxylated
secondary higher alkanol wherein the secondary alkanol has 11 to
lS carbon atoms and the number of moles of ethylene oxide is 9.
Exemplary o~ the aforementioned nonionic surfactants
are Tergitol lS-S-? and Tergitol 15-S-9 (products of Union
Carbide), both of which are linear secondary alcohol ethoxylates.
The former is a condensation product of about 1 mole of a mixture
of secondary higher fatty alcohols averaging 11 to lS carbon
;
2~6~8
atoms with about 7 moles of ethylene oxide, and the latter ia a
condensation 2roduct o~ about 1 mole o~ a mixture of secondar~
~igher 'atty alcohols averaging 11 to 15 carbon atoms with about
9 moles of ethylene oxide. Other suitable surfactants include
Tergitol 15-S-5 (a condensation product of about 1 mole of a
mixture of secondary higher fatty alcohols averaging 11 to 15
carbon atoms with about 5 moles of ethylene oxide) and Tergitol
15-S-12 (a condensation product of about 1 mole of a mixture of
secondary higher fatty alcohols averaging 11 to 15 carbon atoms
with about 12 moles of ethylene oxide).
The polyethoxylated secondary higher alkanols of the
invention may also be utilized with a minor portion of
conventional nonionic surfactants, preferably less than 30% by
weight of the total nonionic surfactants, most preferably less
than 15%.
Such conventional nonionic surfactants include poly-
lower-alkoxylated higher alkanols wherein the alkanol has 8 to 22
carbon atoms, preferably 8 to 18 carbon atoms, most preferably 9
to 15 carbon atoms; and wherein the number of moles of lower
alkylene oxide (of 2 or 3 carbon atoms) is Erom 2 to 20,
preferably 2 to 10, most preferably 2 to 6. Of such materials,
it is preferred to employ those wherein the higher alkanol is a
higher fatty alcohol of 9 to 15 carbon atoms and which contain
from 3 to 6 lower alkoxy qroups per mole; or a mixture of
compounds wherein the higher alkanol is a higher fatty alcohol of
about 16 to 18 carbon atoms and which contain from 5 to 7 lower
alkoxy groups per mole and compounds wherein the higher alkanol
is a higher fatty alcohol of about 9 to 12 carbon atoms and which
contain from 2 to 4 lower alkoxy groups per mole. Most
preferably, there is employed a 50-50 mixture (by weight) of
2Q~60~8
compounds wherein the higher alkanol is a higher fatty alcohol o~
9 to 11 carbon atoms and which contain 2.5 lower alkoxy groups
~er mole and compo ~ds wherein the higher alkanol is a higher
~atty alcohol of 16 to 18 carbon atoms and which contain 6 lower
alkoxy groups per mole.
Exemplary of the aforementioned nonionic surfactants
are Neodol 25-7 and Neodol 23-6.5 (products of Shell), the
former being a condensation product of a mixture of about 1 mole
of a higher fatty alcohols averaging about 12 to 15 carbon atoms
with about 7 moles of ethylene oxide, and the latter being a
condensation product of about 1 mole of a mixture of higher fatt
alcohols averaging about 12 to 13 carbon atoms with about 6.5
moles of ethylene oxide, wherein the higher alcohols are primary
alcohols.
Highly preferred nonionics useful in the present
invention, which are similar ethylene oxide condensation products
of mixtures of primary higher fatty alcohols include: Dobanol
91-5 (Shell), higher fatty alcohols averaging 9 to 11 carbons and
5 moles of ethylene oxide; Dobanol~ 91~2.5 (Shell), higher fatty
alcohols averaging 9 to 11 carbons and 2.5 moles of ethylene
oxide;~Dobanol 45.4 (Shell), higher fatty alcohols averaging 14
to 15 carbons and 4 moles of ethylene oxide; Nacolox~ 810-30
(Condea), higher eatty alcohols averaging 8 to 10 carbons and 3
moIes of ethylene oxide; Nacolox 1012-30 (Condea), higher fatty
alcohols averaging 10 to 12 carbons and 3 moles of ethylene
oxide: Dobanol 25-3 (Shell), higher fatty alcohols averaging 12
to 15 carbons and 3 moles of ethylene oxide; Aeropol 35-7
(Exxon), higher fatty alcohols averaging 13 to 15 carbons and 7
moles of ethylene oxide; Aeropol 91-3 (Exxon), higher fatty
alcohols averaging 9 to 11 carbons and 3 moles of ethylene oxide;
2 ~
and Nacolox~ 1618-60 (Condea), higher fatty alcohols averaging 16
~o 18 carbons and 6 moles of ethylene oxide.
Also useful in the present compositions as a component
o~ 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
~atty alcohol being of 14 to 15 carbon atoms and the number of
ethylene oxide groups per mol being about 11. Such products are
also made by Shell Chemical Company. Another preferred class of
useful nonionics are represented by the commercially well known
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. Examples include the nonionics
sold under the Plurafac trademark of aASF, such as Plurafac RA30,
Plurafac RA40 (a C13-Cls fatty alcohol condensed with 7 moles
propylene oxide and 4 moles ethylene oxide), Plurafac D25 (a C13-
C15 fatty alcohol condensed with 5 moles propylene oxide and 10
moles ethylene oxide), Plurafac B26, and Plurafac RA50 (a mixture
: 20 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~C3H6O)p(C2H4O)qH~
wherein R is a straight or branched primary or secondary
aliphatic hydrocarbon, preferably alkyl or alkenyl, especially
preferably alkyl, of from 6 to 20, preferably 10 to 18,
especially preferably 12 to 18 carbon atoms, p is a number of up
to 14, preferably 3 to 8, and q is a number of up to 14,
2 ~ 8
preferably 3 to 12, can be advantageously used, iow gelling
temperatures are desired.
Furthermore, the compositions of this invention include an
organic solvent or diluent wnicn can runction as a viscosity
control and gel-inhibiting agent for liquid nonionic surface
active agents. Lower (C1-C~ aliphatic alcohols and glycols,
such as ethanol, isopropanol, ethylene glycol, hexylene glycol
and the like have been used for this purpose. Polyethylene
glycols, such as PEG 400, are also useful diluents. Alkylene
glycol ethers, such as the compounds sold under tne trademarks,
Carbopol and Carbitol which have relatively short hydrocarbon
chain lengths (C2-C~) and a low co~tent 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 ethers is disclosed
in the commonly assigned copending application Serial No.
687,815, filed December 31, 1984, 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~H
where R is a C2-C8, preferably C2-C5 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 C2NS-o-cH2cH2oH)~ diethylene glycol
monobutyl ether (C4H9-O-~CH2CH20)2~), tetraethylene glycol
monooctyl ether (C8H17-O-(CH2CH20)4H~, tripropylene glycol
monomethyl ether (CH3-O-(CH (CH3)CH20)30, etc. Diethylene glycol
monobutyl ether is especially preferred.
2~01~8
Another useful anti-gelling agent which is included as
a minor component o~ the liquid phase, is an aliphatic linear or
~liphatic monocyclic dicarboxylic acid, such as the C6 to C12
alkyl and alkenyl derivatives of succinic acid or maleic acid,
and the corresponding anhydrides or an aliphatic monocyclic
dicarboxylic acid compound. The use of these compounds as anti-
gelling agents in non-aqueous liquid heavy duty built laundry
detergent compositions is disclosed in the commonly assigned,
allowed copending application Serial No. 756,334, filed July 18,
1985, the disclosure of which- is incorporated herein in its
entirety by reference thereto.
Briefly, 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 or branched. The aliphatic monocyclic 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 alkyl 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 8 to 13 carbon atoms, especially
preferably 9 to 12 carbon atoms. One of the carboxylic acid
groups (-COOH) 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
2 0 ~ 8
it may be spaced two or three carbon atoms from the ~-posi~ion,
i.e. on the ~- or ~- carbon atoms. The preferred aliphatic
dicarboxylic acids are the ~, ~dicarboxylic acids and the
corresponding anhydrides, and especially preferred are
derivatives of succinic acid or maleic acid and have the general
formula:
Rl-C(H)m-C~ Ri~l(H)m~C \
=c or ~ 0
(H)n~C~C ~---__ OH (H)n-C-C ~=~
wherein Rl is an alkyl or alkenyl group of from about
2 to 10 carbon atoms, preferably 7 to 10 carbon atoms, especiall~
preferably 8 to 10 carbon atoms, wherein n=l and m=0, when --- is
a double bond and n=2 and m=l, when --- is a single bond.
The alkyl or alkenyl group may be straight or branched.
The straight chain alkenyl groups are especially preferred. It
is not necessary that Rl represent a single alkyl or alkenyl
group and mixtures 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 shouId have at least about 6, preferably at
least about 8, especially preferably at least about 10 carbon
atoms and, in total, up to about 22, preferably up to about 18,
especially 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 formula:
11
2 ~
R3~ R2-C~OH
/ COOH
5where -T- represents -CH2~ H=, =CH-, -CH2-CH2- or
-CH=C~-;
R2 represents an alkyl or alkenyl group of from 3 to 12
carbon atoms; and
R3 represents a hydrogen atom or an alkyl or alkenyl
group of f rom 1 to 12 carbon atoms,
--- represents a double or single bond depending on the
nature of the group T,
with the proviso that the total number of carbon atoms
in R2 and R3 is from about 6 to about 22.
Preferably -T- represents -CH2-CH2- or -CH=CH-,
especially preferably -CH=CH-.
R2 and R3 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 R2
and R3 being from about 8 to about 15. The alkyl or alkenyl
groups may be straight or branched but are preferably straight
: chains.
The invention detergent composition may also include
water soluble detergent builder salts. Typical suitable builders
: . ~ :
include, for example, those disclosed in U.S. Patents 4,316,812,
4,264,466, and 3,630,929. Water-soluble inorganic alkaline
builder salts which can be used alone with the detergent compound
or in admixture with other builders are alkali metal carbonate,
borates, phosphates, polyphosphates, bicarbonates, and silicates.
(Ammonium or substituted ammonium salts can also be used.)
Specific examples of such salts are sodium tripolyphosphate,
2 0 ~
sodium carbonate, sodium tetraborate, so~ium pyrophosphatP,
potassium pyrophosphate, sodium bicarbonate, potassium
tripolyphosphate, sodium hexametaphosphate, sodium
sesquicarbonate, sodium mono and diorthophosphate, and potassium
5 bicarbonate. Sodium tripolyphosphate (TPP) is especially
preferred. The alkali metal silicates are useful builder salts
which also ~unction to make the composition anticorrosive to
washing machine parts. Sodium silicates of Na2O/SiO2 ratios of
from 1.6/1 to 1/3.2 especially about 1/2 to 1/2.8 are preferred.
Potassium silicates of the same ratios can also be used.
Another class of builders useful herein are the water-
insoluble aluminosilicates, both of the crystalline and amorphous
type. Various crystalline zeolites (i.e. alumino-silica~ are
described in British Patent 1,504,168, U.S. Patent 4,409,136 and
Canadian Patents 1,072,835 and 1,087,477, all of which are hereby
incorporated by reference for such 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:
~ M2O)x-(Al2o3)y~(sio2)z.wH2o
wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from
1.; to 3.5 or higher and preferably 2 to 3 and W is from 0 to 9,
preferably 2.5 to 6 and M is preferably sodium. A typical
zeollte is type A or similar structure, with type 4A particularly
preferred. The preferred aluminosilicates have calcium ion
exchange capacities of about 200 milliequivalents per gram or
greater, e.g. 500 meqig-
Other materials such as clays, particularly of thewater-insoluble types, may be useful adjuncts in compositions of
this invention. Particularly useful is bentonite. This material
13
2 ~ S ~
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 loosely
combined. The bentonite in its more purified form (i.e. free
from any grit, sand, etc.) suitable for detergents invariably
contains at least 50% montmorillonite ~nd thus its cation
exchange capacity is at least about 50 to 75 meq. per 100 g. of
bentonite. Particularly preferred bentonite are the Wyoming or
Western U.S. bentonites which have been sold as Thixo-jels 1, 2,
3 and 4 by Georgia Kaolin Co. These bentonites are known to
soften textiles as described in British Patent 401,413 to
Marriott and British Patent 461,221 to Marriott and Dugan.
Examples of organic alkaline sequestrant builder salts
whlch can be used alone with the detergent or in admixture with
other organic and inorganic builders are alkali metal, ammonium
or substituted ammonium, aminopolycarboxylates, e.g. sodium and
potassium ethylene diaminetetraacetate (EDTA), sodium and
potassium nitrilotriacetates (NTA) and triethanolammonium N-(2-
hydroxyethyl)nitrilodiacetates. Mixed salts of these
polycarboxylates are also suitable.
Other suitable builders of the organic type include
carboxymethylsuccinates, tartronates and glycollates. Of special
value are the polyacetal carboxylates. The polyacetal
carboxylates and their use in detergent compositions are
described in 4,144,226; 4,315,092 and 4,146,495. Other patents
on similar builders include 4,141,676; 4,169,934; 4,201,858:
4,204,852; 4,224,420; 4,225,685; 4,226,960; 4,233,422; 4,233,423;
4,302,564 and 4,303,777. Also relevant are European Patent
Application Nos. 0015024; 0021491 and 0063399.
2~66~8
Since the compositions of this invention are generally
highly concentrated, and, therefore, may be used at relatively
low dosages, it is desirable to supplement any phosphate builder
(such as sodium tripolyphosphate~ with an auxiliary builder such
as a polymeric carboxylic acid having high calcium binding
capacity to inhibit incrustation which could otherwise be caused
by formation of an insoluble calcium phosphate. Such auxiliary
builders are also well known in the art.
The invention detergent compositions also include a
silicone defoaming composition. Such silicone defoamant
compositions include: Dow Corning DB-100 also known as Dow
Corning antifoam 1400; Thompson-Hayward AFlOOIND and Union
Carbide SAG100. --
2 0 ~
The physical stability of the suspension of thedetergent builder compound or compo~nds and any other suspended
additive, such as sleaching agent, etc., in the liquid vehicle
may be improved ~y the presence o~ a stabilizing agent such as an
aluminum salt of a higher fatty acid.
The 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 fatty acids may also be
used, such as those derived from natural sources, such as tallow
fatty acid, coco fatty acid, etc.
ExampIes of the fatty acids from which the aluminum
salt stabilizers can be formed include, decanolc acid, dodecanoic
acid, palmitic acid, myristic acid, stearic acid, oleic acid,
eicosanoic acid, tallow fatty acid, coco fatty acid, mixtures of
these acids, etc. The aluminum salts of these acids are
generally commercially available, and are preferably used in the
triacid form, e.g. aluminum stearate as aluminum tristearate
~;~ Al(C17H35cOO)3- The monoacid salts, e.g. aluminum monostearate,
Al(OH)2(C17H3sCOO) and diacid salts, e.g. aluminum distearate,
Al~OH)~C17H3sCOO)2, and mixtures 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 above, are
commercially available and can be easily produced by, for
example, saponifying a fatty acid, e.g. animal fat, stearic acid,
16
2 ~
etc., followed by treat~ent of the resulting soap with alum,
alumina, etc. It is presumed that the aluminum salt increases
the wettability of the solid surfaces by the non-ionic
surfactant, which allows the suspended particles to more easily
remain in suspension.
The increased physical stability is manifested by an
increase in the yield stress of the composition by as much as
about 500% or more, for example, in the case of aluminum stearate
by up to about 1000%, as compared to the same composition without
the aluminum stearate stabilizing agent. As described above, the
higher is the yield stress, the higher is the apparent viscosity
at low shear rate and the better is the physical stability.
Only very small amounts of the aluminum salt
stabilizing agent are required to obtain the significant
improvements in physical stability. For example, based on the
total weight of the composition, suitable amounts of the aluminum
salt are in the range of from about 0.1% to about 3%, preferably
from about 0.3% to about 1%.
In addition to its action as a physical stabilizing
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 non-ionic surfactant 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.
While the aluminum salt alone is effective in its
physical stabilizing action, further improvements may be achieved
in certain cases by incorporation of other known physical
stabilizers, such as, for example, an acidic organic phosphorus
2~6~
compound having an acidic -POH group, such as a partial ester of
phosphorous acid and an alkanol.
The acidic organic phosphorus compound may be, for
instance, a partial ester of phosphoric acid and an alcohol such
as an alkanol which has a lipophilic character, having, for
instance, more than 5 carbon atoms, e.g. 8 to 20 carbon atoms.
A specific example is a partial ester of phosphoric
acid and a C16 to Clg alkanol tEmpiphos 5632 from Marchon), it is
made up of about 35~ monoester and 65~ diester.
The inclusion of quite small amounts of the acidic
organic phosphorus compound makes the suspension significantly
more stable against settling on standing but remains pourable,
presumably, as a result of increasing the yield value of the
suspension, while, for the low concentration of stabilizer, e.g.
below about 1%, its plastic viscosity will generally decrease.
It is believed that the use of the acidic phosphorus compound may
result in the formation of a high energy physical bond between
the -POH portion of the molecule and the surfaces of the
inorganic polyphosphate builder so that these surfaces take on an
organic character and become more compatible with the nonionic
surfactant.
The acidic organic phosphorus compound may be selected
from a wide variety of materials, in addition to the partial
esters of phosphoric acid and alkanols mentioned above. Thus,
one may employ a partial ester of phosphoric or phosphorous acid
with a mono or polyhydric alcohol such as hexylene glycol,
ethylene glycol, di- or tri-ethylene glycol or higher
polyethylene glycol, polypropylene glycol, glycerol, sorbitol,
mono or diglycerides of fatty acids, etc. in which one, two or
more of the alcoholic OH groups of the molecule may be esterified
2~6~
with the phosphorous acid. The alcohol may be a non-ionic
surfactant such as an ethoxylated or ethoxylatedpropoxylated
higher alkanol, higher alkyl phenol, or higher alkyl amide. The
-POH group need not be bonded to the organic portion of the
molecule through an ester linkage; instead it may be directly
bonded to carbon (as in a phosphonic acid, such as a polystyrene
in which some of the aromatic rings carry phosphonic acid or
phosphinic acid groups; or an alkylphosphonic acid, such as
propyl or laurylphosphonic acid) or may be connected to the
carbon through other intervening linkages (such as linkages
through O, S or N atoms). ~referably, the carbon:phosphorus
atomic ratio in the organic phosphorus compound is at least abou
3:1, such as 5:1, 10:1, 20:1, 30:1 or 40:1.
Further improvements in the rheological properties of
the liquid detergent compositions can be obtained by including in
the composition a small amount 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 a partial ester of a
nonionic surfactant and a polycarboxylic acid.
The free carboxyl group modified nonionic surfactants,
which may be broadly characterized as polyether carboxylic acids,
function to lower the temperature at which the liquid nonionic
forms a gel with water. The acidic polyether compound can also
decrease the yield stress of such dispersions, aiding in their
dispensibility, without a corresponding decrease in their
stability against settling. Suitable polyether carboxylic acids
contain a grouping of the formula:
R2~0cH2cH2tptocH-cH2tq-y-z-cooH
CH3
2f~6~0~
wherein R2 is hydrogen or methyl, Y is oxygen or sulfur, Z is an
~rganic linkage, p is a positive number of from about 3 to about
,0 and q is zero or a positive number ~f up to 10. Specific
examples include the half-ester of Plurafac RA30 with succinic
anhydride, the half ester of Dobanol 25-7 with succinic
anhydride, etc. Instead of a succinic acid anhydride, other
polycarboxylic acids or anhydrides may be used, e.g. maleic acid,
maleic anhydride, glutaric acid, malonic acid, succinic acid,
phthalic acid, phthalic anhydride, citric acid, etc.
Furthermore, other linkages may be used, such as ether, thioether
or urethane linkages, formed by conventional reactions. For
instance, to form an ether linkage, the nonionic surfactant may
be treated with a strong base (to convert its OH group to an ONa
group for instance) and then reacted with a halocarboxylic acid
such as chloroacetic acid or chloropropionic acid or the
corresponding bromo compound. Thus, the resulting carboxylic
acid may have the formula R-Y-Z-COOH where R is the residue of a
nonionic surfactant (on removal of a terminal OH), Y is oxygen or
sulfur and Z represents an organic linkage such as a hydrocarbon
group of, say, one to ten carbon atoms which may be attached to
the oxygen (or sulfur) of the formula directly or by means of an
intervening linkage such as an oxygen-containing linkage, e.g. a
O or O , etc.
-CO- -C-NH-
The polyether carboxylic acid may be produced from a
polyether which is not a nonionic surfactant, e.g. it may be made
by reaction with a polyalkoxy compQund such as polyethylene
glycol or a monoester or monoether thereof which does not have
the long alkyl chain characteristic of the nonionic surfactant.
20~60a8
Thus, R may have the formula R2
Rl(ocH-cH2)n-
where R2 is hydrogen or methyl, R1 is alkylphenyl or alkyl or
other chain terminating group and "n" is at least 3 such as 5 to
25. When the alkyl of Rl is a higher alkyl, R is a residue of a
nonionic surfactant. As indicated above, Rl may instead be
hydrogen or lower alkyl (e.g. methyl, ethyl, propyl, butyl) or
lower acyl (e.g. acetyl, etc.). The acidic polyether compound if
present in the detergent composition, is preferably added
dissolved in the nonionic surfactant. Various other detergent
additives or adjuvants may be present in the detergent product t
give it additional desired properties, either of functional or
aesthetic nature. Thus, there may be included in the
formulation, minor amounts of soil suspending or anti-
redeposition agents, e.g. polyvinyl alcohol, ~atty amides, sodium
carboxymethyl cellulose, hydroxy-propyl methyl cellulose; optical
brighteners, e.g. cotton, polyamide and polyester brighteners,
for example, stilbene, triazole and benzidine sulfone
compositions, especially sulfonated substituted triazinyl
stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone,
etc., most preferred are stilbene and triazole combinations.
Bluing agents such as ultramarine blue; enzymes,
preferably proteolytic enzymes, such as subtilisin, bromelin,
papain, trypsin and pepsin, as well as amylase type enzymes,
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 C12 to C22 alkyl alcohol with C12 to Clg
2 ~ 8
alkylsulfate, pH modifiers and pH buffer~; color safe bleaches
and perfume.
The bleaching agents are classified broadly for
convenience, as chlorine bleaches and oxygen bleaches. Chlorine
bleaches are typified by sodium hypochlorite (NaOCl), potassium
dichloroisocyanurate (59% available chlorine), and
trichloroisocyanuric acid (95% available chlorine). Oxygen
bleaches are preferred and are represented by percompounds which
liberate hydrogen peroxide in solution. Preferred examples
include sodium and potassium perborates, percarbonates, and
perphosphates, and potassium monopersulfate. The perborates,
particularly sodium perborate monohydrate, are especially
preferred.
The peroxygen compound is preferably used in admixture
with an activator therefor. Suitable 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 4,430,244, the relevant disclosures of
which are incorporated herein by reference. Polyacylated
compounds are preferred activators; among these, compounds such
as tetraacetyl ethylene diamine (nTAEDn) and pentaacetyl glucose
are particularly preferred.
Other useful activators include, for example,
~acetylsalicylic acid derivatives, ethylidene benzoate acetate and
its salts, ethylidene carboxylate acetate and its salts, alkyl
and alkenyl succinic anhydride, tetraacetylglycouril (nTAGUn),
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.
~ 0 ~ 8
The bleach activator usually interacts with the
peroxygen compound to form a peroxyacid bleaching agent in the
wash water. It is ?referred 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,
at 25C, in water, of an ionic strength of 0.1 mole~liter, pK
being conventionally defined by the formula: pK = -log K where
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 diethylene triamine pentaacetic acid (DETPA);
diethylene triamine pentamethyl phosphonic acid (DTPMP); and
ethylene diamine tetramethylene phosphonic acid (EDITEMPA).
In order to avoid loss of peroxide bleaching agent,
e.g. sodium perborate, resulting from enzyme-induced
decomposition, such as by catalase enzyme, the compositions may
additionally include an enzyme inhibitor compound, i.e. a
compound capable of inhibiting enzyme-induced decomposition of
the peroxide bleaching agent. Suitable inhibitor compounds are
disclosed in U.S. Patent 3,606,990, the relevant disclosure of
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, suitable amounts of the hydroxylamine salt
inhibitors can be as low as about 0.01 to 0.4%. Generally,
20~60~
however, suitable amounts of enzyme inhibitors are u? to ~bout
15~, for example, 0.1 to 10%, by weight of the co~position.
In a ~referred form of the invention, the mixture of
liquid ingredients and solid ingredients is subjected to an
attrition type of mill in which the particle sizes of the solid
ingredients are reduced to less than about 10 microns, e.g. to an
average particle size of 2 to 10 microns or even lower (e.g. 1
micron). Preferably less than about 10%, especially less than
about 5% of all the suspended particles have particle sizes
greater than 10 microns. Compositions whose dispersed particles
are of such small size have improved stability against separatio
or settling on storage. It is found that the acidic polyether
compound can decrease the yield stress of such dispersions,
aiding in their dispensibility, without a corresponding decrease
in their stability against settling,
It has been found that the order of addition of
materials to the mixture will affect the properties of the
mixture, especially the defoamer efficacy. More particularly,
silicone defoamers which do not contain colloidal silica must be
pre-mixed into the nonionic surfactant before the solvent and
di~acid in order to retain their anti-foaming properties.
Silicone defoamers that do contain colloidal silica are
relatively unaffected by order of addition.
Accordingly, for silicone defoamers which do not
contain colloidal silica, the nonionic surfactant is first
admixed with the silicone composition, this admixture is then
admixed with the solvent, that admixture is then admixed with the
diacid, and the resultant admixture can then be blended with the
remaining ingredients.
24
2~g~8
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 liquid. Mi~lls which employ grinding balls
(ball mills) or similar mobile grinding elements have given very
good results. Thus, one may use a laboratory batch attritor
having 8 mm diameter steatite grinding balls. For larger scale
work a continuously operating mill in which there are 1 mm or 1.5
mm diameter grinding balls working in a very small gap between a
stator and a rotor operating at a relatively high speed (e.g. a
CoBall mill) may be employed; when using such a mill, it is
desirable to pass the blend of liquids and solids 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 about 40 microns) prior to the step of grinding to an average
particle diameter below about 10 microns in the continuous ball
mill.
In the preferred heavy duty liquid detergent
compositions of the invention, typical proportions (based on the
total composition, unless otherwise specified) of the ingredients
are as follows:
nonionic surfactant, within the range of about 20 to 70
wt %, preferably about 22 to 60 wt %
solvent, up to 20 wt % with the weight ratio of
nonionic surfactant to solvent in the range of from 100:1 to 1:1,
preferably up to 15 wt % with the weight ratio of nonionic
surfactant to solvent in the range of from 50:1 to 2:1;
diacid, within the range of about 0 to 30 wt %,
preferably 1.5 to 15 wt %;
20~6~8
builder salt(s), within the range of about 10 to 60 wt
%, preferably 20 to 50 wt ~; and
silicone defoamant composition, within the range of
about 0.5 to 1.5 wt %.
; The aluminum salt of the higher aliphatic fatty acid
may be present in an amount of at least 0.1~, preferably from
about 0.1 to about 3%, more preferably from about 0.3 to about
1%.
The polyether carboxylic acid gel-inhibiting compound,
may be present in an amount of up to an amount to supply in the
range of about 0.5 to 10 parts (e.g. about 1 to 6 parts., such as
about 2 to 5 parts) of -COOH (M.W. 45) per 100 parts of blend of
such acid compound and nonionic surfactant. Typically, the amount
of the polyether carboxylic acid compound is in the range of
about 0.01 to 1 part per part of nonionic surfactant, such as
about 0.05 to 0.6 part, e.g. about 0.2 to 0.5 part;
Acidlc organic phosphoric acid compound, as anti-
settling agent; up to 5%, for example, in the range of 0.01 to
5%, such as about 0.05 to 2~, e.g. about 0.1 to 1~.
Suitable ranges of the optional detergent additives
are: enzymes - 0 to 2%, especially 0.7 to 1.3%; corrosion
inhibitors - about 0 to 40~, and preferably 5 to 30%; 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%, preferably 0.5 to 5%;
colorants, perfumes, brighteners and bluing agents total weight
% to about 2% and preferably 0% to about 1%; pH modifiers and pH
buffers - 0 to 5%~ preferabIy 0 to 2%; bleaching agent - 0% to
; about 40% and preferably 0% to about 25%, for example 2 to 20~;
bleach stabilizers and bleach activators 0 to about 15%,
26
2~66~08
bleach stabilizers and bleach activators 0 to about 1i%,
preferably 0 to 10%, for example, 0.1 to 8~, enzyme-inhibitors
- 0 to 15~, tor example, 0.01 to 15%, preferably 0.1 to 10%;
sequestering agent of high complexing 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 constituents of the detergent
composition.
In this application, all proportions and percentages
are by weight unless otherwise indicated. In the examples,
atmospheric pressure is used unless otherwise indicated.
It is understood that the foregoing detailed
description is given merely by way of illustration and that
variations may be made therein without departing from the spirit
of the invention.
Example 1
The compositions set forth in Table 1 were prepared and
Ross-Miles foam heights for each system were determined, the
results are set forth in Table 2.
20~6~08
Table_l
j Run NABLD _ontrol ~ 3
ISurfactant 36.5(1) 33(2) 32(2) 32(2)
¦Butyl Carbitol ' 10 10 10 10
Diacid(3) , 2 2 2 2
Na TriDolYPhos~hate I 29.5 33 33 ' 33
Na Perborate Monohydrate I 9 _ 9 9 9
!TAED _ , 4.5 4.5 _ 4.5 4.5
Defoamer ¦ - - 1 0(4) 1 0(5)
. __ . _
Minor A ditives g.s. 9-5- 9 5 __ g.s.
(1) Lutensol 400 (BASF) - a linear ethylene oxide/propylene
oxide nonionic
(2) 1:1 mixture of Tergitol 15-S-7 and Tergitol 15-S-9
(3)
(4? Dow-Corning DB-100
(5) Thompson-Hayward AF-IND-100
Table 2(1)
Run Ross-Miles Foam Height (mm)
0 Min. 5 Min
. . j
NABLD 80 1 50
Control 1105 _ 11 - as-so _
I A 15 1 0
I B I 10-15 0
__. ._
(1) Room Temp.; 0.5~ sol'ns.; 300 ppm European Hardness
28
20~0~8
The tests indicate superior ~oam inhibition and foam
breaking for the two formulations with antifoams (A and B)
despite the increased foaming exhibited by the Control as
compared to the conventional formulation (NABLD)
Additionally, side-by-side Miele machine wash tests
confirmed that (a) foam levels were acceptable in the defoamer-
containing products during the wash cycle, and (b) foam levels in
the cold-water rinse cycles (where residual surfactant generates
high foam levels) were noticeably less dense for products with
defoamers.
Example 2
Compositions having the formulation shown in Table 3
were prepared by a "Post-Addition" technique and a "Pre-Addition'
technique.
Table 3
Ingredient %
_~ (by wt)
Surfactant(l) 74
Cosolvent(2) 21
Diacid(3) 4
~ Defoamer
I ~ (1) 1:1 mixture of Tergitol 15-S-7 and
Tergitol- 15-S-9
(2)
(3)
(The post-addition technique comprised admixing the surfactant,
cosolvent and diacid; and then mixing in the defoamer.
The pre-addition technique comprised admixing the surfactant and
the defoamer; then mixing in the cosolvent; and then mixing in
the diacid.)
29
2 ~ 8
The Ross-Miles foam height was then determined for each
of the compositions according to Table 3. The results are shown
in Table 4.
Table 4
Ross-Miles Foam Height (mm)
¦ Defoamer ¦ Post-Addition Pre-Addition
l l O Min. 1 5 Min. O Min. 5 Min.
! . ,
¦ SAG 10(1) ' 95 1 75 25 15
i SAG 47(2) _ ~ 100 , 40 25 17
SAG 100(3) ; 90 35 10 0
SAG 471(4) 75 15 40 15
SENTRY(5) 95 45 15 15
(1)
(2)
(3j
(4)
(S)
