Note: Descriptions are shown in the official language in which they were submitted.
1049367
BACKGROUND OF THE INVENTION
The present invention relates to heavy duty liquid
detergent compositions containing nonionic surfactants,
ethanolamine-neutralized anionic surfactants, free
ethanolamine and a polymeric soil release agent. As used
herein, the term "liquid" encompasses semi-liquid or gel
compositions, as well as more conventional freely-flowing
formulations.
Heavy duty liquid detergent compositions are well-
known in the art. Usually such compositions (see, forexample, U.S. Patents 2,908,651; 2,920,045; 3,272,753,
3,393,154; and Belgian Patents 613,165 and 665,532)
contain a synthetic organic detergent component which is
generally anionic, nonionic, or mixed anionic-nonionic in
nature; an inorganic builder salt; and a solvent, usually
water and/or alcohol. These compositions frequently
contain a hydrotrope or solubilizing agent to permit the
addition of sufficient quantities of surfactant and
builder salt to provide a reasonable volume/usage
performance ratio. While such liquid detergent
compositions have been found effective for some types of
home laundering, alternative compositions which do not
contain inorganic builder salts are of current interest
and are being developed to replace built compositions on a
broad scale.
Attempts have been made to formulate builder-free,
hydrotrope-free liquid detergent compositions. For
example, U.S. Patent 3,528,925 discloses substantially
anhydrous liquid detergent compositions which consist of
an alkyl aryl sulfonic acid, a nonionic surface active
agent and an alkanolamine component. U.S. Patent
10493~7
2,875,153 discloses liquid detergent compositions
containing a nonionic surfactant component and a sodium
soap component. U.S. Patent 2,543,744 discloses a
low-foaming dishwashing composition comprising a nonionic,
water-soluble, synthetic detergent and a water-soluble
soap in the form of an alkali metal, ammonium or amine
salt. U.S. Patent 3,663,445 pertains to liquid detergent
compositions which contain anionic and nonionic sur-
factants in combination with certain ethanolamime
compounds.
Attempts have also been made to provide compounds
capable of conferring soil release properties to fabrics
woven from hydrophobic fibers, particularly
1049367
polyester. These synthetic fabrics are frequently co-
polymers of ethylene glycol and terephthalic acid, and are
sold under a number of trademarks, e.g., Dacron ~ , Fortrel ,
Kodel ~ and Blue C Polyester ~ As a result of the hydro-
phobic character of the~e fabrics, their laundering (particularly
as regards oily soil and oil stains) is difficult because of
the reduced wettability of the fibers. Since the inherent
character of the fabric itself is hydrophobic, or oleophilic,
once an oily soil or oily stain is deposited on the fabric,
either by normal use or by accident, the oily soil or oily
stain tends to be "attached" to the surface of the fiber.
As a result, the oily soil or stain is difficult to remove in
the laundering process.
Due to the fact that synthetic polyester and poly-
ester-blend fabrics (e.g. polyester-cotton blends) are sus-
ceptible to oil staining and, once stained, are difficult to
clean, manufacturers of synthetic fabrics and blends have
sought to increase the hydrophilic character of the polyester
to provide ease of laundering.
A number of approaches for enhancing the hydrophilic
character of polyester fabrics and blends have been employed.
These methods often involve a process carried out by the textile-
fiber manufacturer or the textile manufacturer; see Imperial
Chemical, Netherlands Application 65/09456, published January
24, 1966; see also D. A. Garrett and P.N. Hartley, J. Soc.
Dyers and Colourists, 82, 7, 252-7 (1967) and Chem. Eng. News,
- 44, 42-43 (October 17, 1966).
Other polyester fabric finishing techniques involving
detergent compositions are described in : German Patent
1,194,734; Fiber Ind. Inc., Netherlands application 65/02428,
published August 26, 1965; Belgian Patent 641,882; and French
patent 1,.394,401. U.S. Patent 3,416,952 relates to a
"- 1049367
modifying treatment for polyester fibers whereby a poly-
ethylene terephthalate polymer is applied to the surface of
said fabrics. Such polymers contain ethylene terephthalate
and polyethylene oxide terephthalate units at a molar ratio
from 2:1 to 6:1. British Patent 1,175,207 discloses a
process for treating filaments and fibers by contacting
same with polyesters containing from about 10% to about 50%
by weight of crystalline polyester segments which are identical
with the repeat units forming the crystalline segment of the
polyester fiber, and from about 90% to about 50~ by weight
of water solvatable polyoxyalkylene ester segments. The
polymers employed appear to be identical to those disclosed
- in U.S. Patent 3,416,952, above. British patent 1,092,435,
deals with a stable dispersion of water-insoluble graft
polymers containing polyoxyethylene glycol and polyethylene
terephthalate . These particular polymers have a ratio of
ethylene terephthalate to polyoxyethylene terephthalate from
about 2:1 to about 6:1. The teachings of British patent
1,119,367 and Imperial Chemical, Dutch Patent application
66/14134 published April 10, 1967 relate to the application
of surface modifying agents to fibers as described in the ~-
patents referred to hereinabove.
U.S. Patent 3,712,873 discloses the use of certain
polyester polymers in combination with quaternary ammonium
salts as fabric treatment compositions. Polymers having a
molecular weight in the range from 1,000 to 100,000, and a
molar ratio of terephthalic acid : polyglycol : glycol from
4.5 : 3.5 : 1, are disclosed. U.S. Patent 3,959,230, issued
July 8, 1975, to Basadur, relates to compositions and pro-
cesses for imparting renewable soil release finish to poly-
ester-containing fabrics. Polymers based on terephthalic
A
.
1049367
acid, ethylene glycol and polyethylene oxide and their use
in acidic fabric rinses are disclosed. The polymers have
a molecular weight in the range from 1,000 to 100,000, and
the polyethylene oxide lin~ has a molecular weight of 1300
to 1800.
U.S. Patent 3,959,230, issued May 25, 1976 to Hugh R.
Hays, discloses terephthalate polymers composed of ethylene
terephthalate and polyethylene oxide terephthalate capable of
imparting soil-release properties to synthetic fibers treated
with a dilute aqueous solution of said polymers. These
polymers also fall within the broad class of polymeric soil
release agents of the type used in the instant compositions.
In contrast with the prior art soil release polymers, the Hays'
polymers are said to be especially useful in solid, dry
detergent compositions; see Nicol and Hays, U.S. Patent
3,962,152, issued June 8, 1976.
While a variety of polymeric soil release agents are
known, there seems to have been little or no attempt to
optimize the detergent compositions used in conjunction with
such agents. This is due to the heretofore unrecognized
fact that certain types of soil release agents exhibit
outstanding cleaning performance only when combined with
specific detersive ingredients. It has now been found that,
by selecting the proper detersive ingredients, liquid
detergents containing any of the foregoing types of ester
soil release polymers can be used to provide superior cloan-
sing of oily soils and stains.
It is a primary object of this invention to provide
heavy duty liquid dete~gent compositions which exhibit
excellent cleanina performance while concurrently imparting
soil release properties to hydrophobic fabrics treated
therewith.
~A
~049367
It is another object of this invention to provide
heavy duty liquid detergent compositions comprising
mixtures of nonionic surfactants, anionic surfactants, and
ethanolamines in combination with polymeric soil-release
ingredients.
It is a further object of this invention to provide
heavy duty liquid detergent compositions comprising
soil-release polymers having various molar ratios of
ethylene terephthalate to polyethylene oxide.
The above and other objects are met by formulating
liquid detergent compositions containing mixtures of
nonionic and anionic surface-active agents, free ethanol-
amines and polymers composed of terephthalate esters, as
described hereinafter.
The compositions herein are adapted for use both in a
standard through-the-wash cleansing operation or as a
pretreatment whereby the composition is applied directly
to a heavily soiled fabric, which is subsequently
laundered.
SUMMARY OF THE INVENTION 7
This invention encompasses heavy duty liquid detergent
compositions capable of providing improved cleaning
performance and simultaneously imparting soil release
properties to fabrics treated therewith. Such compo-
sitions comprise:
(a) from about 15% to about 65%, preferably about 30%
to about 60%, by weight of a water-soluble nonionic
surfactant produced by the condensation of an alkylene
oxide, preferably ethylene oxide, with an organic
hydrophobic compound;
(b) from about 10% to about 40%, prefeLably 20% to -~
.~- . - - . , . ~ -
1049367
30%, by weight of a water-soluble ethanolamine-
neutralized anionic surfactant;
(c) at least 1%, preferably from about 3~ to about
15% by weight, of free ethanolamine, and
(d) from about 0.15% ~o about 25~ by weight of a
polymer comprising ethylene terephthalate and
polyethylene oxide terephthalate, wherein said polymer
comprises from about 25~ to about 50% by total weight
ethylene terephthalate units, wherein said poly-
ethylene oxide terephthalate contains polyethylene
oxide units having a molecular weight of from about
300 to about 10,000, the total molecular weight of
said polymer being in the range from about 5,000 to
about 200,000.
Optionally, and in a preferred mode, the compositions
herein contain a water-dispersible liquid carrier.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The compositions of the instant invention comprise
(1) a nonionic surfactant; (2) an ethanolamine-neutralized
anionic surfactant; (3) free ethanolamine; (4) a soil-
release polymer composed of ethylene terephthalate and
polyethylene oxide terephthalate; and preferably (5) a
liquid carrier. Each of these ingredients is discussed in
detail hereinafter.
Unless otherwise indicated, the term "%" as used
herein represents percent-by-weight.
Nonionic Surfactant
From about 15% to about ~5% of the liquid detergent
comositions of the present invention comprise a nonionic
surfactant produced by the condensation of an alkylene
oxide, especially ethylene oxide (hydrophilic in nature)
104936'7
with an organic hydrophobic compound, which is usually
aliphatic or alkyl aromatic in nature. The length of the
hydrophilic polyoxyalkylene moiety which is condensed with
any particular hydrophobic compound can be readily adjusted
to yield a water-soluble compound having the desired degree
of balance between hydrophilic and hydrophobic properties.
Examples of suitable nonionic surfactants herein include:
(1) The polyethylene oxide condensates of alkyl phenols.
These compounds include the condensation products of alkyl
phenols having an alkyl group containing from about 6 to 12
carbon atoms in either a straight chain or branched chain
configuration with ethylene oxide, said ethylene oxide being
present in an amount equal to 5 to 25 moles of ethylene oxide
per mole of alkyl phenol. The alkyl substituent in such
compounds can be derived, for example, from polymerized
propylene, diisobutylene, and the like. Examples of
compounds of this type include nonyl phenol condensed with
about 9.5 moles of ethylene oxide per mole of nonyl phenol;
dodecyl phenol condensed with about 12 moles of ethylene
oxide per mole of phenol; dinonyl phenol condensed with about
15 moles of ethylene oxide per mole of phenol; and di-
isooctylphenol condensed with about 15 moles of ethylene
oxide per mole of phenol. Commercially available nonionic
surfactants of this type include Igepal ~ Co-630 marketed
by the GAF Corporation; and Triton ~ X-45, X-114, X-100 and
X-102, all marketed by the Rohm and Haas Company.
(2) The condensation Froducts of aliphatic alcohols with
ethylene oxide. The alkyl chain of the aliphatic alcohol can
be either straight or branched and generally contains from
about 8 to about 22 carbon atoms. ~xamples of such
ethoxylated alcohols include the condensation product of
1049367
about ~ moles o~ ethylene oxide with 1 mole of tridecanol;
myristyl alcohol condensed with about 10 moles of ethylene
oxide per mole of myristyl alcohol; the condensation
product of ethylene oxide with coconut fatty alcohol
wherein the coconut alcohol is a mixture of fatty alcohols
with alkyd chains varying from 10 to 14 carbon atoms in
length and wherein the condensate contains about 6 moles
of ethylene oxide per mole of alcohol; and the condensa-
tion product of about 9 moles of ethylene oxide with the
above-described coconut alcohol. Examples of commercially
available nonionic surfactants of this type Tergitol~
15-S-9 marketed by Union Carbide Corporation, Neodol~9
23-6.5 marketed by Shell Chemical Company and Kyr ~ EOB
marketed by The Procter & Gamble Company.
13) The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene
oxide with propylene glycol. The hydrophobic portion of
these compounds has a molecular weight of from about 1500
to 1800 and, of course, exhibits water insolubility. The
addition of polyoxyethylene moieties to this hydrophobic
portion tends to increase the water-solubility of the
molecule as a whole, and the liquid character of the
product is retained up to the point where the polyoxy-
ethylene content is about 50% of the total weight of the
condensation product. Examples of compounds of this type
include certain of the commercially available Pluronic@~
surfactants marketed by Wyandotte Chemicals Corporation.
(4) The condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and
ethylene diamine. The hydrophobic moiety of these
products consists of the reaction product of ethylene
.. ~ . .
. . . . .
- 1049367
diamine and excess propylene oxide, said moiety having a
molecular weight of from about 2500 to about 3000. This
hydrophobic moiety is condensed with ethylene oxide to the
extent that the condensation product contains from about
40% to about 80% by weight of polyoxyethylene and has a
molecular weight of from about 5,000 to ahout 11,000.
Examples of this type of nonionic surfactant include
certain of the commercially available Tetronic@~ com-
pounds marketed by Wyandotte Chemicals Corporation.
In the detergent compositions of the instant invention
it is preferred that the particular nonionic surfactants
employed have a hydrophilic-lipophilic balance (HLB) of
from about 8 to about 15. A highly preferred nonionic
surfactant within this range is the condensation product
of 6 moles of ethylene oxide with coconut fatty alcohol
(HLB = 12).
Another preferred nonionic surfactant herein com-
prises a mixture of "surfactant" and "co-surfactant" as
described in Canadian application Serial No. 210,835,
filed October 7, 1974.
The term "nonionic surfactant as employed herein
encompasses these preferred mixtures of Collins.
The presence of the nonionic surfactant in the instant
liquid detergent compositions provides oily stain removal
in both pre-treatment application and wash water utiliza-
tion of the instant compositions. The nonionic surfac-
tants also contribute to the physical stability of the
liquid detergent compositions herein.
Anionic Surfactant
Another essential component of the instant composi-
tions is an ethanolamine-neutralized anionic surface-active
-- 10 --
~049367
agent. This anionic component is used in an amount from
about 10% to about 40% of the total compositions herein.
The ethanolamine salts are prepared by neutralizing the
corresponding anionic detergent acids with an ethanolamine
selected from the groùp consisting of monoethanolamine,
diethanolamine and triethanolamine.
Examples of anionic detergent acids suitable for use
in the compositions of this invention, after neutraliza-
tion with ethanolamine, include higher fatty acids
containing from about 8 to about 24 carbon atoms and
preferably from about 10 to about 20 carbon atoms.
Suitable fatty acids can be obtained from natural sources
such as plant or animal esters (e.g. , palm oil, coconut
oil, babassu oil, soybean oil, castor oil, tallow, whale
and fish oils, grease, lard, and mixtures thereof). The
fatty acids also can be synthetically prepared, e.g., by
the oxidation of petroleum, or by hydrogenation of carbon
monoxide by the Fischer-Tropsch process. Resin acids are
suitable, such as rosin and those resin acids in tall
oil. Naphthenic acids are also suitable. Particularly
useful are mixtures of fatty acids derived from coconut
oil and tallow. The ethanolamine salts can be made by
direct saponification of the fats and oils or by direct
neutralization of the free fatty acids which are prepared
in a separate manufacturing process.
The ethanolamine salts of organic sulfuric reaction
products having in their molecular structure an alkyl
moiety containing from about 8 to about 22 carbon atoms
and a sulfonic acid or sulfuric acid ester radical can
also be used. (Included in the term "alkyl" is the alkyl
portion of higher acyl radicals.) Preferred are the
~0493~7
anionic acids obtained by sulfating higher alcohols
(8 - 18 carbon atoms) produced by reducing glycerides of
tallow or coconut oil, and alkyl benzene sulfonic acids in
which the alkyl group contains from about 9 to about 15
carbon atoms, in straight chain or branched chain config-
uration. Especially useful are linear straight chain
alkyl benzene sulfonic acids in which the average of the
alkyl groups is about 12 carbon atoms; alkyl glyceryl
ether sulfonic acids, especially those ethers of higher
alcohols derived from tallow and coconut oil; coconut oil
fatty acid monoglyceride sulfonic acids and sulfuric acid
esters; and akyl phenol ethylene oxide ether sulfuric acid
esters with about 1 to about lO units of ethylene oxide
per molecule and in which the alkyl groups contain about 8
to about 12 carbon atoms.
Ethanolamine-neutralized anionic phosphate surfactants
containing an oxyacid of phosphorus as the anionic
solubilizing group are also useful. The more common
solubilizing groups, of course, are -SO4H, -SO3H, and
-CO2H.
Alkyl phosphate esters such as (R-O)2PO2H and
ROP03H2 in which R represents an alkyl chain con-
taining from about 8 to about 20 carbon atoms are useful.
These esters can also be modified by including in the
molecule from one to about 40 alkylene oxide units, e.g.,
ethylene oxide units. Formulae for these modified
phosphate anionic acids are
,
[ R
- 12 -
: .
::
1049367
o
( 2 2 )n]
O-H
in which R resresents an alkyl group containing from about
8 to 20 carbon atoms, or an alkylphenyl group in which the
alkyl group contains from about 8 to 20 carbon atoms, and
in which n is an integer from 1 to about 40.
Another class of suitable anionic detergent acids
particularly useful in this invention when ethanolamine-
neutralized includes the 2-acyloxy-alkane-1-sulfonic acids.
These compounds have the formula
O
1 0 OCR2
Rl - CH - CH2SO3H
where Rl is alkyl of about 9 to about 23 carbon atoms (forming
with the two carbon atoms an alkane group); and R2 is alkyl
of 1 to about 8 carbon atoms.
Specific examples of beta-acyloxy-alkane-l-sulfonic
acids (also known as 2-acyloxy-alkane-1-sulfonic acids)
utilizable herein include 2-acetoxy-tridecane-1-sulfonic
acid; 2-propionyloxytetradecane-1-sulfonic acid; 2-butanoyloxy-
tetradecane-l-sulfonic acid; 2-pentanoyloxy-pentadecane-1-
sulfonic acid; 2-acetoxy-hexadecane-1-sulfonic acid; 2-
octanoyloxy-tetradecane-l-sulfonic acid; 2-acetoxy-
heptadecane-l-sulfonic acid; 2-acetoxy-octadecane-1-sulfonic
acid; 2-acetoxy-nonadecane-1-sulfonic acid; 2-acetoxy-
eicosane-l-sulfonic acid; and 2-propionyloxy-docosane-1-
sulfonic acid.
Preferred beta-acyloxy-alkane-l-sulfonic acids
correspond to the above formula wl~erein Rl is an alkyl of
about 12 to about 16 carbon atoms.
- 13 -
`- 1049367
Belgium Patent 650,323 discloses the preparation of
certain 2-acyloxy alkanesulfonic acids.
Anotner class of anionic detergent acids which are
useful herein as the ethanolamine salts include the beta-
alkyloxy alkane sulfonic acids. These compounds have the
following formula:
OR H
1 2
R - f c So3H
H H
where Rl is a straight chain alkyl group having from 6 to 20
carbon atoms and R2 is a lower alkyl group having from 1 to
3 carbon atoms.
Specific examples of beta-alkyloxy alkane sulfonic
acids or alternatively 2-alkyloxy-alkane-1-sulfonic acids,
utilizable herein to provide superior cleaning and whitening
levels under household washing conditions include:
; beta-methoxydecanesulfonic acid,
beta-methoxy-tridecanesulfonic acid,
beta-ethoxytetradecanesulfonic acid,
beta-isopropoxyhexadecanesulfonic acid,
beta-tert-butoxytetradecanesulfonic acid,
beta-methoxyoctadecanesulfonic acid, and
beta-n-propoxydodecanesulfonic acid.
Other anionic detergènt acids which, when ethanolamine
neutralized, are preferred for use in the compositions of
the instant invention include alkyl ether sulfuric acid
esters and "olefin sulfonic acids".
The preferred alkyl ether sulfuric acid esters have
the formula
(C2 4 )xS3H
wherein R is alkyl or alkenyl of about 10 to about 20 carbon
- 14 -
__ .. . . . .. _ .
1049367
atoms, and x is 1 to 30.
Es~ecially preferred are those alkyl ether sulfuric
acid esters wherein R has from about 14 to about 1~ carbon
atoms and wherein x has an average value of about 1 to
about 6. Specific examples of especially preferred species
include: coconut alkyl ethylene glycol sulfuric acid ester;
tallow alkyl trioxyethylene sulfuric acid ester; tallow
alkyl pentaoxyethylene sulfuric acid ester; tetradecyl
pentaoxyethylene and lauryl hexaoxyethylene sulfuric acid
esters.
The preferred "olefin sulfonic acids" for use herein
in ethanolamine neutralized form have from about 12 to
abou-t 24 carbon atoms in the alkyl portion of the molecule.
Such materials can be produced by sulfonation of ~-olefins
by means of uncomplexed sulfur dioxide followed by neutraliza-
tion with ethanolamine under conditions such that any
sultones present are hydrolyzed to the corresponding hydroxy-
alkane sulfonates. The ~-olefin starting materials preferably
contain from 14 to 16 carbon atoms. The preferred ~-olefin
sulfonates are described in great detail in U.S. Patent
3,332,880, Adriaan Kessler, et al., patented July 2S, 1~67.
Examples of preferred ~-olefins include l-tetradecene,
l-hexadecene, l-octadecene and mixtures thereof. As noted,
the anionic acids are neutralized with an ethanolamine
neutralizing agent selected from the group consisting of
monoethanolamine, diethanolamine, triethanolamine and
mixtures thereof.
Triethanolamine is the preferred ethanolamine herein;
hence, the triethanolamine salts of tne foregoing surfactant
acids are preferred in the present compositions.
1049367
~ree Ethanolamine Component
The liquid detergent compositions of the present
invention contain from about 3% to about 15%, preferably
from about 5~ to about 15%, of free ethanolamine. The
ethanolamine useful herein is selected from the group con-
sisting of monoethanolamine, diethanolamine, triethanolamine,
and mixtures thereof. Triethanolamine is preferred.
Mixtures of these ethanolamine compounds are produced by
the reaction of ethylene oxide with ammonia. T;le pure
compounds can be separated from this mixture by standard
distillation procedures. The free ethanolamine contributes
to detergency performance and serves as a buffering agent
which maintains wash water pH of the instant compositions
within the range of from about 7 to about 9.
Soil Release Polymer
As a further essential ingredient, the compositions
of the instant invention contain from about 0.15% to about
25% preferably from about 1% to about 15%, more preferably
from about 5~ to about 10%, of a soil release polymer
containing ethylene terephthalate groups having the formula:
[OCH2CH2OC ~ C -] ; and
polyethylene oxide terephthalate groups having the formula:
[ (OCH2CH2) nOC ~ 1C--]
wherein total weight of the ethylene terephthalate units in
- 16 -
104~367
the polymer (i.e., including those from the polyethylene
oxide terephthalate) is from about 25% to 50% and preferably
from about 30% to 40% of the polymer. The molecular weight
of the polyethylene oxide linking unit is in the range from
about 300 to about lO,000, preferably from about 400 to
about 4,000, i.e., n in the above formula is an integer of
from about 7 to about 220. The polymers have an overall
molecular weight in the range from about 5,000 to about
200,000, preferably from about 25,000 to about 70,000. The
polymers are also characterized by a random polymer structure,
i.e., all possible combinations of ethylene terephthalate
and polyethylene oxide terephthalate can be present.
Examples of the polymers which are useful herein
appear in Table I.
- 17 -
~04g367
~D o
oo~ oo
OD O
C~o n
OD .0
~ I a~ ~ ~
o
. .
:
'~ '
~
~ H . .
~ ml 1~~ 1n ~ Ln O ' ~
- In
, .
.
CO
~1 o ~ o
. ~1 '
' ' .'
. ~
X o d~
O-- ~ W
o
W-lW~l O
o ~ ~ ~ X W
5 ~ 5 E~ E~ 5 0
-- 18 --
'
~ 1049367
The soil release polymers herein are substantive to
hydrophobic fabrics, particularly polyesters, under laundry
rinse conditions, apparently because of the presence of
the hydrophobic ethylene oxide terephthalate groups.
The soil release polymers used in this invention can
be prepared by conventional polymerization processes known
in the art. As an example, the process described in the
specification of British Patent 1,119,367 can be used for
preparing operable polymers herein by selecting the proper
monomer precursors. Preferred polymers for use herein
are prepared according to the following technique: 194 g.
dimethyl terephthalate, 67 g. etnylene glycol, 420 g.
polyethylene oxide (molecular weight 600); 0.44 g. 2,6-di-
tert-buty1-4-methylphenol; 0.0776 g. antimony trioxide;
and 0.3024 g. calcium acetate are mixed in a suitable
reaction vessel and heated to 210C with stirring over a
1.5 hour period. During this time, methanol and some
dimethyl terephthalate are distilled from the reaction
vessel. The reaction temperature is then raised to 280C
and maintained at this temperature for two hours. Following
addition of 0.282 g. of a 24.8% solution of phosphorous
acid in ethylene glycol to the foregoing reaction mixture,
a stream of nitrogen is blown over the reaction mixture
and allowed to exhaust for two hours. Dispersions of the
polymer prepared in this manner can be made by mixing the
molten polymer with water in a Waring blender.
In the preparation of the above polymers the nitrogen
exhaustion preferably lasts from about two hours to about
2 1!2 hours. Lowering the nitrogen exhaustion to about
1.5 hours or increasing it to about 3.0 hours adversely
affects the soil-release characteristics of the operable
polymers.
-- 19 --
~04C~367
Processin~
The present compositionscan be formulated by preparing
each component separately and thoroughly mixing them to-
gether in any order. In a preferred method for preparing
the instant compositions, the anionic detergent and tne
ethanolamine components are formulated simultaneously by
over-neutralizing mixtures of the anionic detergent acid
with the ethanolamine. This method forms the requisite
ethanolamine-neutralized anionic surface-active agent in situ
and also provides the free ethanolamine component of the
instant composition.
When this preferred composition formulation method is
utilized, the total amount of the ethanolamine employed will
vary with the nature and proportion of the particular
anionic detergent acid and with the particular ethanolamine
employed. A highly preferred ethanolamine concentration
for formulation of the anionic-ethanolamine portion of the
composition is that ethanolamine weight percentage which is
approximately equal to the weight percent of anionic
surfactant mixture (on a free acid basis) present in any
given detergent compositions of the instant invention.
By adding this preferred amount, the ethanolamine will
always be present in greater than stoichiometric amount
for com~lete neutralization of the acid mixture and will
provide the requisite excess free ethanolamine no matter
which ethanolamine and which anionic acid mixture is used,
within the limits of the present invention.
Liquid Carrier
Although the present liquid detergent compositions
need only contain the above-described components (i.e.,
anhydrous compositions), and are liquid in this form due
- 20 -
1049367
to the fluidity of the nonionics and ethanolamines, highly
preferred compositions of tne present invention contain,
in addition to these active components, a liquid carrier
selected from the group consisting of water and water-
alcohol mixtures. Generally, sucn liquid carriers can be
employed to the extent of from about 1% to 4~% by weight
of the total detergent compositions. Preferred compositions
comprise from about 25% to 45% by weight of a liquid carrier.
The carriers herein are solvents for the active
ingredients, and use of such solvents provides several
advantages. First, the physical stability of the detergent
compositions is improved since clear points can thereby be
lowered to provide compositions which do not cloud at lower
temperatures which might be encountered during shipping or
storing of commercially marketed detergent compositions.
Secondly, addition of solvents, especially water-alcohol
mixtures, serves to regulate the gelling tendency wnich
liquid detergent compositions of the instant type exhibit
upon dilution with water.
- 20 When an alcohol-water mixture is employed as a solvent,
the weight ratio of water to alcohol preferably is maintained
above about 3:1, more preferably from about 4:1 to about 7:1.
Alcohol (particularly ethanol) concentrations higher tnan
this in water-alcohol mixtures used in the instant invention
are preferably avoided because of flammabi~ity problems
which arise at higher alcohol levels.
Any alcohol containing from 1 to about 5 carbon atoms
can be employed in the water-alcohol carrier mixture when
such mixtures are utilized in the instant detergent com-
positions. Exam~les of operable alcohols include methanol,
ethanol, propanol, isopropanol, butanol, isobutanol, and
- 21 -
: .
1049367
pentanol. From a toxicological standpoint, ethanol is
hi~hly preferred.
Anti-Gelling A~ent
Another o~tional component which can be added to tne
detergent compositions of the instant invention comprises an
electrolyte salt. Addition of an electrolyte salt serves
to lessen gel formation which tends to occur upon dilution
of the instant detergent compositions with water. When
used in combination with a water-alconol solvent, from
about 0.5% to 5~ by weight of an electrolyte salt completely
eliminates gel formation without the need for alcohol levels
which exceed flammability safety levels.
Suitable electrolyte salts include the alkali metal,
chlorides, sulfates and carbonates, and the salts formed
from the reaction of ethanolamines with formic, acetic,
propionic, butyric, citric or sulfuric acid. Specific
examples of such salts include sodium chloride, potassium
chloride, sodium carbonate, potassium carbonate, potassium
sulfate, sodium sulfate, triethanolamine sulfate, triethanol-
amine citrate, triethanolamine acetate, triethanolamineformate, monoethanolamine propionate and diethanolamine
butyrate. Potassium chloride is highly preferred as an
anti-gellant when employed in the instant compositions at
concentrations of from about 1% to 3% by weight.
As noted, the employment of a liquid carrier solvent
and electrolyte controls gel formation in the instant liquid
detergent compositions. If, however, gel formation is
desired, it is possible to select particular concentrations
of a water carrier which yield gelled compositions in the
absence of alcohol and electrolyte salt. (As noted, a gel
composition is a "liquid" for purposes of this invention.)
iO49367
Thus, compositions containing the three active components in
the above-specified concentrations and a water solvent
comprising from about 15% to 35% by weight can be gelled,
provided no alcohol or electrolyte is present.
Adjunct Com~onents
Other optional non-essential, non-interfering com~onents
can be added to the instant compositions to provide improved
performance or aesthetic appeal. Preferred compositions of
the invention are those to which a color stabilizing agent
such as citric acid has been added. These compositions
- exhibit surprising stability against the tendency of such
;~ compositions to develop a reddening upon storage. In addition,
the presence of citric acid in the compositions of the
invention has a beneficial effect from the standpoint of
preventing the development of the stains observed on the
outer surfaces of plastic bottles and occasioned by spillage,
seepage, or handling of bottles with hands previously con-
tacted with the compositions of the invention. As with the
anionic surfactant acids, the citric acid forms ethanolamine
citrate when added to the instant compositions containing
excess ethanolamine. For convenience, this ethanolamine
citrate concentration in the compositions is expressed as
a weight percentage of the free acid form of the citrate,
i.e., citric acid, added to the compositions. An amount of
citric acid of up to about 1% by weight of composition is
generally added to obtain these color benefits. A highly
preferred range for the added citric acid is from about
0.05% to about 0.10~ by weight of composition.
Other optional components include brighteners, fluores-
cers, enzymes, bleaching agents, anti-microbial agents,
corrosion inhibitors and coloring agents. Such components
'.
- 23 -
~04936~7
usually comprise no more than about 3~ by weight of the
total composition.
Employment of ethanolamine salts and excess ethanolamine
contributes to the effectiveness of the instant detergent
compositions. For example, these compositions containing
the ethanolamine counterion in combination with excess free
ethanolamine are much superior in cleaning polyester/cotton
than corresponding compositions containing the more conven-
tional sodium or potassium salts of the anionic surfactant
acids and no free ethanolamine.
Preferred Surfactant Compositions
.
As can be seen from the foregoing, a wide variety of
nonionic surfactants can be combined with a wide variety
of ethanolamine-neutralized anionic surfactants and a free
~'.
- 24 -
1049367
ethanolamine, most preferably in combination with a liquid
carrier, and employed with the soil-release polymers herein
to provide highly improved heavy-duty liquid detergent
compositions. Remarkably, the compositions herein provide
excellent cleaning performance without the need for deter-
gency builders, such as the phosphates, nitrilotriacetates,
and the like. While there are various useful combinations
of nonionic/ethanolamine-neutralized anionic/ethanolamine
detergent compositions, the compositions disclosed in
Canadian patent 1,020,039, issued November 1, 1977 and
in Canadian Patent 992,835, issued July 13, 1976, are
particularly adapted for use in combination with the soil-
release polymers herein.
More specifically, these preferred compositions are
as follows. The first type of composition contains certain
specific C14 to C16 ethoxylated nonionic surfactants which
provide stable compositions particularly adapted for either
through-the-wash or pretreatment fabric cleansing. In
general, such compositions comprise from about 25% to about
40% by weight of a nonionic surfactant derived by the con-
densation of from 5 to 10 moles of ethylene oxide with an
alcohol containing from 14 to about 16 carbon atoms. Such
compositions additionally contain an ethanolamine-
neutralized anionic surfactant of the type disclosed herein-
above in an amount sufficient to provide a
2~
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weight ratio of nonionic surfactant to anionic surfactant
within the range o~ from about 1.8:1 to about 3.5:1, based
on the free acid form of the anionic surfactant. The
compositions additionally contain ethanolamine material,
preferably triethanolamine, in an amount sufficient to
provide at least 1% by weight of the composition of free
ethanolamine.
The second type of composition particularly useful
herein comprises from about 30% to about 60% by weight of
a nonionic surfactant of the type disclosed hereinabove,
and is not particularly limited to the nonionic sur-
factants produced from the C14-C16 alcohols employed
in the compositions hereinabove. These compositions
additionally contain an anionic surfactant mixture present
in a quantity sufficient to provide a weight ratio of
nonionic surfactant to anionic surfactant mixture in its
free acid form of from about 2.5:1 to about 3.5:1. Such
anionic surfactant mixtures comprise an ethanolamine-
neutralized alkyl benzene sulfonate having from about 9 to
about 15 carbon atoms in the alkyl chain and an
ethanolamine-neutralized soap (i.e., fatty acid salt)
containing from about ~ to about 24, preferably from about
10 to about 22, carbon atoms in the fatty acid moiety of
said soap. The anionic surfactant mixture containing the
sulfonate and soap is formulated to provide a weight ratio
of the acid form of the sulfonate to the acid form of the
soap of from about 20:1 to about 1:1. Such compositions
additionally contain a free ethanolamine, preferably
triethanolamine, in an amount which comprises at least 1%
by weight of the total composition.
As noted, these preferred compositions contain the
essential mixture of nonionic, ethanolamine-neutralized
2B
.
~049367
anionic and free ethanolamine compound now found to be
particularly useful in combination with polymeric ester
soil-release agents herein. The major difference between
the two types of preferred compositions herein is that, in
the first, proper selection of the relatively long-chain
nonionic surfactants within a narrow range permits the
formulation of storage-stable compositions without the
need for the presence of fatty acid (soaps). In the
second type of preferred composition, the fatty acid is
present to provide long-term storage stability.
The compositions of this invention are used in two
different ways for fabric cleaning. 1hey can be used as
pre-treatment agents which are applied in concentrated
form directly onto fabric stains prior to laundering in an
aqueous bath. The compositions are also useful as
detergents for conventional fabric laundering operations.
Stain removal, soil removal and soil release properties
are attained when the instant compositions are employed in
an aqueous laundering liquor at a concentration of about
0.10% by weight (approximately 1/4 cup per 17-19 gallons
of wash water).
The compositions of the instant invention are far
superior to similar liquid detergent compositions which do
not contain the soil release polymer, and are especially
useful for removing oil from hydrophobic fibers in the
wash water of a standard home laundering process. Deter-
gency performance is also superior to that attained with
conventional built granular anionic detergent compositions.
The following examples illustrate the liquid detergent
compositions of the instant invention:
A liquid detergent composition is prepared by mixing
the following components:
27
1049367
~ EXAMPLE I
_ .
Component Wt %
Condensation product of coconut alcohol
with 6 moles of ethylene oxide 33
Triethanolamine linear dodecyl benzene 16.5
sulfonate
- Oleic acid triethanolamine salt 1,5
Free triethanolamine 5
Ethanol 6
10 Potassium chloride 2
Soil Release Polymer A* 5
Water and minor ingredients Balance to 100
* From Table I
Desized 4 inch square polyester swatches (Dacron )
either prewashed with the compositions of this invention or
untreated are soiled hy depositing 0.1 ml. liquid soil (bacon
grease, CriscoR oil or dirty motor oil) in the center of
the swatch. The soiled swatches are allowed to wick for
18 hours at ambient conditions, whereafter they are washed
20 in an automatic washer for 10 minutes in 7 grain, 105F
water containing 1000 ppm of the above composition. The
oily stain removal i5 substantially greater than that
achieved under identical washing conditions using analogous
liquid compositions which do not contain the soil release
polymer.
Substantially the same results are achieved when soil
release polymers B through E set forth in Table I are used
in the above composition in levels of 5% and 10% (wt.)
-Improved release of oily soil is also achieved at levels
of the above polymers of 0.2% and 25%, by weight.
Substantially similar results are obtained when the
.
~049367
free triethanolamine is replaced by an equivalent amount
of free monoethanolamine and free diethanolamine, respectively.
Substantially comparable results are also obtained
when the triethanolamine linear dodecyl benzene sulfonate
is replaced by an equivalent amount of the triethanolamine
salts of: coconut alkyl ethylene glycol sulfuric acid
ester; tallow alkyl pentaoxyethylene sulfuric acid ester;
tetradecyl pentaoxyethylene and lauryl hexaoxyethylene
sulfuric acid esters, respectively.
The foregoing composition is stable on storage. Equally
stable compositions are secured by replacing the oleic acid
triethanolamine salt by an equivalen~ amount of the mono-,
di- and triethanolamine salts of lauric acid, myristic
acid, palmitic acid, stearic acid and mixed tallowalkyl
acids, respectively.
EXAMPLE II
One hundred grams of a heavy duty liquid detergent
composition are formulated having the following composition:
Component Wt.%
C14_15 (EO)7 * 33.0
Triethanolamine salt of linear alkyl benzene
sulfonic wherein the alkyl chain averages
12 carbon atoms in length ** - 24.2
Triethanolamine (free) 3.7
Ethanol 2.0
Potassium chloride 2.5
Soil Release Polymer A *** 5.0
Brightener, perfume, dye 0.2
Water Balance
* Commercially available as Neodol 45-7
** Prepared by admixing 16.5 g. of C alkylbenzene
sulfonic acid and 11.0 g. trietha~olamine.
*** From Table I.
29
1~19367
The weight ratio of nonionic surfactant to anionic
surfactant (on a free acid basis) in the foregoing composi-
tion is 2.00:1.
The foregoing composition is a stable (i.e., does not
separate or otherwise degrade on storage and is satisfactory
for use after being subjected to a freeze-thaw cycle) clear
liquid detergent which does not gel upon dilution with
water. The composition provides level medium-high sudsing
in wash water of varying temperature and hardness. The
foregoing composition provides improved pre-treatment and
through-the-wash fabric detergency.
The foregoing composition is modified by the addition
of 0.05~ of citric acid. The color stability of the
composition containing citric acid is markedly improved
over similar compositions without citric acid.
In the above composition the triethanolamine-neutralized
anionic surfactant is replaced by the mono-ethanolamine- and
diethanolamine-neutralized anionic surfactant, respectively,
and good overall detergency is secured.
In the above composition the free triethanolamine is
replaced by free monoethanolamine and free diethanolamine,
respectively, and good overall detergency is secured.
1049367
EXAMPLE III
Component Wt.%
Condensation product of average 7 moles
of ethylene oxide with C14_15 synthetic
alcohol 40.0
Triethanolamine salt of linear alkylbenzene
sulfonic acid wherein the alkyl chain
averages 12 carbons in length 19.8
Free triethanolamine 5.0
10 Ethanol 5.0
Potassium chloride 2.5
Minors (brighteners, color stabilizers,
perfume, coloring agents) 0.9
Soil Release Polymer B * 0.9
Water Balance
Weight ratio of nonionic surfactant to
anionic surfactant (on an anionic free
acid basis) 3~03
* From Table I
The foregoing composition is stable and provides
excellent fabric cleaning when used either full strength
as a pre-treatment or for through-the-wash detergency at
a level of 1/4 cup/17 gallons of wash water.
: 31
~.
~049367
EY~MPLE IV
Component % Wt.
Condensation product of average 7 moles
of ethylene oxide with C~4_15 synthetic
alcohol 33.0
Triethanolamine salt of linear alkylbenzéne
sulfonic acid wherein the alkyl chain
averages 12 carbons in length 19.8
Free triethanolamine 5.0
10 Ethanol 5.0
Potassium chloride 2.5
Minors (brighteners, color stabilizers,
perfume, coloring agents) 0.9
Soil Release Polymer C * 1.2
Water Balance
Weight ratio of nonionic surfactant to
anionic surfactant (on an anionic free
acid basis) 2.50
* From Table I
The foregoing composition is stable and provides
excellent fabric cleaning when used either full strength
as a pre-treatment or for through-the-wash detergency at
a level of 1/4 cup/17 gallons of wash water.
32
1049367
EXAMPLE V
Component ~ wt.
Condensation product of average 9 moles of
ethylene oxide with C14 15 synthetic
alcohol 28.0
Triethanolamine salt of linear alkylbenzene
sulfonic acid wherein the alkyl chain
averages 12 carbons in length 19.2
Free triethanolamine 3.7
10 Ethanol 5.0
Potassium chloride 2.5
Minors (brighteners, color stabilizers,
perfume, coloring agents) 0.9
Soil Release Polymer D * 10.0
Water Balance
Weight ratio of nonionic surfactant to
anionic surfactant (on an anionic free
acid basis) 2.0
* From Table I
The foregoing composition is stable and provides
excellent fabric cleaning when used either full strength
: as a pre-treatment or for through-the-wash detergency at
~ a level of 1/4 cup/17 gallons of wash water.
~: 33
1049367
EXAMPLE VI
Component % Wt.
Condensation product of average 6 moles of
ethylene oxide with C14 15 synthetic
Triethanolamine salt of linear alkylbenzene
sulfonic acid wherein the alkyl chain
averages 12 carbons in length 16.5
Free triethanolamine 6.0
10 Ethanol 5.0
Potassium chloride 2.5
Minors (brighteners, color stabilizers,
perfume, coloring agents) 0.9
Soil Release Polymer E * 2.0
Water Balance
Weight ratio of nonionic surfactant to
anionic surfactant (on an anionic free
acid basis) 3.0
*From Table I
The foregoing composition is stable and provides
excellent fabric cleaning when used either full strength
as a pre-treatment or for through-the-wash detergency at
a level of 1/4 cup/17 gallons of wash water.
34
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