Note: Descriptions are shown in the official language in which they were submitted.
20~1716
LIQUID SOFTE~ING AND ANTI-STATIC
NONIONIC DETERGENT COMPOSITION WITH
SOIL RELEASE PROMOTING PET-POET COPOLYMER
BACKGROUND OF THE INVENTION
I Field of the Invention:
I
¦ This invention relates to a detergent-softening
S ¦ composition. More specifically, the present inventlon relates to
¦ softening/anti-static compositions adapted for use in the wash
¦ cycle of a laundering operation, the composition including as
¦ essential ingredients a nonionic detergent, an anionic detergent,
¦ a cationic fabric softener-anti-static agent and a soil release
¦ promoting polymer of the polyethylene terephthalate-
¦ polyoxyethylene terephthalate (PET-POET) type.
I Description of the Prior Art:
I
Compositions useful for treating fabrics to improve
the softness and feel characteristics thereof are known in the
art.
When used in domestic laundering, the fabric softeners
are typically added to the rinse water during the rinse cycle
having a duration of only from about 2 to 5 minutes.
Consequently, the consumer is required to monitor the laundering
operation or take other precautions so that the fabric softener
is added at the proper time. This requires the consumer to
return to the washing machine either just prior to or at the
beginning of the rinse cycle of the washing operation which is
obviously burdensome to the consumer. In addition, special
prec~ution has to be taken to use a proper amount of the fabric
softener so as to avoid over dosage which may render the clothes
water repellant by depositing a greasy film on the fabric
surface, as well as imparting a certain degree of yellowness to
he fabrlcs.
,.,- ~
2011716 ;
As a solution to the above-noted problems, it has been
known to use fabric softeners which are compatible with common
laundry detergents so that the softeners can be combined with the
detergents in a single package for use during the wash cycle of
the laundering operation. Examples of such wash cycle added
fabric softening compositions are shown in U.S. Patents
3,351,438, 3,660,286 and 3,703,480 and many others. In general,
these wash cycle fabric softening compositions contain a cationic
quaternary ammonium fabric softener and additional ingredients
which render the softening compounds compatible with the common
laundry detergents.
It is also known, however, that the cationic softening
compounds added to the wash cycle, either as an ingredient in a
detergent-softener composition or as a wash cycle softener,
interfere with the brightening activity, as well as the cleaning
efficiency of the detergent. As a result, it has been sought to
offset to some degree this interference in detergent-softening
compositions by using nonionic surfactants, higher levels of
brightener compound, carboxymethylcellulose, anti-yellowing
compounds, bluing agents and so forth. However, little
improvement has been made in wash cycle softening compositions
using a variety of detergents, most of which are anionics.
There have been many disclosures in the art relating to
detergent compositions containing cationic softening agents,
including the quaternary ammonium compound softening agents, and
nonionic surface-active compounds. As representative of this
art, mention can be made of U.S. Patents 4,264,4S7; 4,239,659;
4,259,217; 4,222,905; 3,951,879; 3,360,470; 3,351,483; 3,644,203;
etc. In addition, U.S. Patents 3,537,993; 3,583,912; 3,983,079;
4,203,872, and 4,264,479, speciflcally disclose combinations of
~'
-~ -
2~417~
nonionic surface-active agent, cationic fabric softener and
another ionic surfactant or modifier, such as zwitterionic
surfactants, amphoteric surfactants, and the like.
While many of these prior art formulations provide
satisfactory cleaning and/or softening under many different
conditions they still suffer from the defects of not providing
adequate softening - e.g. comparable to rinse cycle - added
softeners.
U.S. Patent 3,920,565 discloses a liquid rinse cycle
fabric softener composition containing 2 to 15% of a cationic
fabric softener and 0.5 to 4.0% of an alkali metal salt of a
fatty acid of from 16 to 22 carbon atoms (soap) and optionally,
up to 2~ of a nonionic emulsifier, the balance water. The di-
higher alkyl dimethyl ammonium chlorides are the preferred
cationics, although mono-higher alkyl quats are also mentioned.
It is generally accepted in the art that the mono-
higher alkyl quaternary ammonium compounds, such as, for example,
stearyltrimethyl ammonium chloride, being relatively water-
soluble, are less effective softeners that the di-higher alkyl
cationic quaternary softeners (see, for example, U.S. Patent
4,326,965), and, therefore, their use in conjunction with, for
example, anionic detergents, such as fatty acid soaps, with which
they are capable of forming softening complexes has been
suggested for use as rinse cycle fabric softeners.
The present inventor previously discovered that stable,
fabric softening compositions having improved dispersibility in
cold water as used in the rinse cycle, are provided by a cationic
quaternary ammonium compound, as the sole softener, and an
anionic sulfonate at a weight ratio of cationic to anionic of
from about 80:1 to 3:1 (see U.S. Patent 3,997,453). This patent
2 0 ~
discloses both mono-higher and di-higher alkyl cationic
quaternary softening compounds and also discloses alkyl benzene
sulfonates as the anionic compound. According to this patent,
the addition of minor amounts of the anionic sulfonate to water
dispersions of the excess amount of quaternary softener reduces
the viscosity of the dispersion and produces a homogeneous liquid
which is readily dispersible in cold water ~i.e. the rinse cycle
of an automatic washing machine).
As mentioned above, however, it has been recognlzed for
some time that it would be highly desirable as a matter of
convenience to employ the fabric softening formulation
concurrently with the detergent in the wash cycle of the washing
machine.
U.S. Patent 4,222,905 to Cockrell, Jr. discloses
lS laundry detergent compositions which may be in liquid form and
which are formulated from certain nonionic surfactants and
certain cationic surfactants, including mono-higher alkyl
quaternary ammonium compounds, such as tallowalkyltrimethyl
ammonium halide, at a nonionic:cationic weight ratio of from 5:1
to about 1:1. This patent teaches that the amount of anion-
producing materials should be minimized and preferably totally
avoided, but in any case, anionic materials having a dissociation
constant of less than 1 x 10-5, such as sodium Cll.g linear
alkylbenzene sulfonate, should be eontained only in amounts up to
10%, by weight, of the eationie surfaetant.
Nonionie/eatlonic mixed surfactant detergent
compositions having a nonionic:cationic weight ratio of from
about 1 1 to 40:1 in which the nonionic surfaetant is of the
class having a hydrophilic-lipophilic balance ~HLB) of from about
5 to about 17, and the cationic surfactant is of the class of
~;
~ 2~71~
mono-higher alkyl quaternary ammonium compounds in which the
higher alkyl has from about 20 to about 30 carbon atoms, are
disclosed by Murphy in U.S. Patent 4,239,659. This patent
provides a general disclosure that other adjunct components may
be included in their conventional art-established levels for use
which is stated to be from about 0 to about 40%. A broad list of -
adjunct components is given including semi-polar nonionic,
anionic, zwitterionic and ampholytic cosurfactants, builders,
dyes, fillers, enzymes, bleaches, and many others. There are no
examples using, and no disclosure of, anionic surfactants,
however, it is stated that the cosurfactants must be compatible
with the nonionic and cationic and can be any of the anionics
disclosed in U.S. Patent 4,259,217 to Murphy.
This latter Murphy patent discloses surfactant mixtures
of nonionic surfactants having an ~LB of from about 5 to about 17
and a cationic surfactant, inclusive of mono-higher alkyl
quaternary ammonium compounds, at a nonionic:cationic weight
ratio of from 5.1:1 to about 100:1. According to this patent,
the detergent compositions may contain up to about 50%,
preferably from about 1 to about 15%, of anionic surfactants
and/or zwitterionic surfactants. The anionic surfactants
include, among others, linear alkyl benzene sulfonates and alkyl
ether sulfates. Example XV in column 40 of this patent
describes a heavy duty liquid laundry detergent composition of
the following formula:
~ 6
20~17~6
Component Weight .
Sodium sulfate of C12_15 alcohol 5.0
ethoxylated with 3 moles of ethylene oxide
C12_13 alcohol ethoxylate containing an 20.0
5 average of 6.5 moles ethylene oxide
Coconutalkyltrimethyl ammonium chloride 3.5
Glycine 8.0 .
Sodium toluene sulfonate 10.0
Wa~er and minors ~alance ~o 100. .
The following heavy duty liquid detergent composition .
is shown in Example XVII (column 41):
Component Weight
Condensate of C 4-1 fatty alcohol with 28.5
an average of ~ mo~es of ethylene oxide
Triethanolamine sa~t of linear alkylbenzene 20.0
sulfonic acid wherein the alkyl chain has :.
an average of 11.9 carbon atoms
C8h~8 aidkYldihYdrXYethYl methyl ammonium 1.5 .
Ethanol 10.0
Diethylenetriamine pentamethyl phosphonic 0.3
acid
Citric acid 0.2
9.1 mixture of dimethylpolysiloxane and 0.3 .
acrogel silica emulsified in highly
ethoxylated fatty acid (commercially
available from Dow Corning as DB31)
Saturated fatty acid having from 16 to 2~ 0.75
carbon atoms in the alkyl chain
Proteolytic enzyme 0.4
Minor adjuvants and water salance to 100.
A liquid laundry detergent and fabric softener
composition which contains about 3-35~ by weight of a nonionic
. 2~17~6
surfactant, about 3-30% by weight mono-higher alkyl quaternary
amnnonium compound cationic surfactant and a mixture of anionic
surfactants including (a) C4-Clo alcohol sulfates and (b) C12-
C22 alcohol ethoxylated ether sulfates or carboxylates is
disclosed in U.S. Patent 4,264,457 to seeks and Wysocki. The
mole ratio of total cationic surfactant to total anionic
surfactant can vary rom 0.8:1 to 10:1. According to the
patentees, the selection of and proportions of the two specific
anionic surfactants to the exclusion of other known anionic
surfactants is essential to obtain the maximal effectiveness for
detergency, softness and anti-static properties.
The present inventor has also previously discovered
that softening and anti-static performance of a detergent
compound and a cationic mono-higher alkyl quaternary ammonium
compound fabric softening agent is significantly enhanced by
using the cationic softener as an approximately 1:1 complex with
an anionic surfactant which is a linear alkyl aromatic sulfonate.
This discovery is the subject matter of Applicant's copending
application Serial No. 661,775, filed October 17, 1984, the
disclosure of which is incorporated herein by reference.
Furthermore, this enhancement of the softening/anti-static
performance was achieved without sacrificing, and in some cases,
with significant improvement in the whitening and cleaning
performance.
While excellent softening and anti-static benefits
have been provided by the liquid nonionic detergent compositions
base~ on the complex of the cationic fabric softener and linear
alkyl benzene sulfonate, the present inventor has also previously
discovered that further improvements in overall cleaning
performance and the ability to form complexes of the mono-higher
2~71fi
alkyl quaternary fabric softener with a broader range of
commercially available anionic detergents can both be attained by
aclding to the composition an additional surfactant compound which
is a sulfosuccinamate compound. This discovery is the subject
matter of Applicant's copending Serial No. 873,486, filed June
12, 1986, the disclosure of which is incorporated herein by
reference. The incorporation of the sulfosuccinamate compound
significantly boosts detergency of the nonionic/cationic mixture
with or without the additional benefits of other anionic
surfactants.
The use of polyethylene terephthalate-polyoxyethylene
terephthalate (PET-POET) soil release promoting polymers is well
documented in the patent literature. Representative examples of
the patent literature disclosing the use of PET-POET and similar
polymers in the treatment of synthetic textile materials, in
general, and in laundry detergent compositions, in particular,
include, among others, U.S. Patents 3,557,0i9 (and its
corresponding sritish Patent Specification 1,088,984); 3,652,713;
3,723,568; 3,959,230; 3,962,152; 4,125,370; 4,132,680; 4,569,772;
and British Patent Specifications 1,154,370; 1,317,278;
1,377,092; and sritish Published Patent Application 2,123,B48 A.
U.S. Patent 3,557,039 to ~cIntyre et al. shows the
preparation of such copolymers by the ester interchange and
subsequent polymerization of dimethyl terephthalate ~DMT) and
ethylene glycol (EG) in the presence of a mixed catalyst system
of calcium acetate hemihydrate and antimony trioxide. A similar
reaction is shown in U.S. Patent 3,959,280 to Hays, this patent
further using polyethylene oxide as one reactant in addition to
DMT and EG monomers. The PET-POET copolymers of Hays are
characterized by a molar ratio of ethylene terephthalate units to
~,r-
20~1716
po]yethylene oxide terephthalate units of from about 25:75 to
about 35:6S, by the polyethylene oxide of the polyethylene oxide
terephthalate having a molecular weight of from about 300 to 700,
by a molecular weight of about 25,000 to about 55,000, and by a
melting point below 100C.
U.S. Patent 3,652,713 forms antistatic fibers, films
and other shaped articles from compositions in which polyethylene
terephthalate is mixed with a polyether-polyester block copolymer
such that the polyether segment constitutes from 0.1 to 10.0~ by
weight based on the total weight of the mixture. The polyether-
polyester block copolymer can be prepared by melt-polymerizing
(condensation polymerization).polyethylene terephthalate of
number average molecular weight of from 1,000 to 2,000 with
polyethylene glycol having a number average molecular weight of
lS from 1,000 to 50,000 at a highly reduced pressure and elevated
temperature in the presence of antimony trioxide and trimethyl
phosphate.
According to British 1,317,278 to Ambler et al. high
molecular weight ~e.g., spinning-grade or film-forming)
polyethylene terephthalate is reacted with polyethylene glycol
(MW = 300 to 30,000) at temperatures in the range of 100C to
300C, preferably at atmospheric pressure in the presence of
conventional ester exchange catalyst, for example, antimony
oxides, calcium acetate, tetralkyltitanates and stannous
octoate.
U.S. Patent 4,125,370 to Nicol discloses PET-POET soil
release promoting random copolymers having an average molecular
weight in the range of about 5,000 to about 200,000, with a molar
ratio o~ ethylene terephthalate to polyethylene oxide
terephthalate of from about 20:80 to 90:10, the polyethylene
2~7~fi
oxide linking unit having a molecular weight in the range from
about 300 to 10,000. These polymers can be prepared according to
the procedure disclosed in the aforementioned Patent 3,959,280 to
Hays or by the process described in U.S. Patent 3,479,212 to
Robertson et al.
PET-POET soil release promoting polymers are also
commercially available, for example, the products Alkaril QCJ and
QCF from Alkaril Chemicals, Inc.; Milease T from ICI America; and
2elcon from E. I. duPont de Nemours & Co.
While satisfactory soil release promoting property has
been obtained from the commercially available products and as
described in the literature, there have been problems with regard
to the stability, as well as effectiveness, of these copolymers
during storage and under actual use conditions. Thus, U.S.
lS Patent 4,125,370 teaches providing a concentration of certain
hardness ions to promote deposition of the soil release polymers
on the fabrics being washed and to promote soil release
performance. U.S. Patent 4,569,772 teaches that detergent
compositions containing PET-POET polymers tend to lose their soil
release promoting properties on storage, if the compositions
contain alkaline builders. The patentees overcome this tendency
by co-melting the PET-POET copolymer with a water-soluble alkali
metal polyacrylate and converting the melt to solid particles.
~ritish Published Patent Application 2,123,848 A overcomes this
tendency by uniformly distributing the PET-POET copolymer
throughout the particulate detergent product by preparing
particles of a builder or a mixture of builders for a non-ionic
detergent, dissolving and/or dispersing in such non-ionic
detergent in liquid state a substantially anhydrous soil release
promoting PET-POET polymer, and spraying such liquid non-ionic
- 20~17:~6
detergent-polymer mixture onto moving surfaces of the builder
particles to distribute such non-ionic detergent and polymer over
suc:h particles.
While excellent softening and anti-static benefits have
been provided by the liquid non-ionic detergent compositions
based on the complex of the cationic fabric softener and anionic r
detergents such as linear alkyl benzene sulfonate, and while
stable compositions of PET-POET polymers with non-ionic
detergents have been achieved, there still exlsts a problam of
incompatibility when formulating liquid detergents containing
both cationic fabric softeners and commercially available PET-
POET soil release promoting copolymers. In particular, when a
commercially available PET-POET soil release promoting copolymer,
such as Alkaril QCJ, is added to a liquid detergent containing a
non-ionic surfactant and an anionic surfactant, the liquid is
slightly turbid, but the suspension is stable over time. When a
cationic fabric softener is added to this liquid, the suspension
becomes unstable, and a fine precipitate settles out over a
period of time. This fine precipitate considerably degrades the
appearance of the product to the consumer, especially when
packaged in translucent containers and subjected to long-term
storage prior to sale.
SUMMARY OF THE INVENTION
As a result of the inventor's further research, it has
now been discovered that a stable liquid detergent composition
contalining both cationic fabric softener and PET-POET soil
release promoting copolymer can be attained by utilizing a water-
soluble fraction of the conventional PET-POET copolymer in lieu
of the conventional PET-POET copolymer when formulating the
liquid detergent.
2~ 17~6
Accordingly, it is an object of this invention to
improve the soil release performance of detergent compositions
con~aining non-ionic detergent compositions, anionic detergent
compositions, and cationic fabric softener-anti-static agents.
It is another object of this invention to formulate
stable, liquid detergent compositions using non-ionic detergent
compositions, anionic detergent compositions, cationic fabric
softener-anti-static agents and PET-POET-type soil release
promoting copolymers.
These and other objects of the invention which will
become apparent hereinafter are achieved by providing an aqueous
laundry detergent composition-useful for washing and softening
soiled fabrics comprising a nonionic detergent, an anionic
detergent, a cationic fabric softener-anti-static agent and a
water-soluble fraction of a polyethylene terephthalate-
polyoxyethylene terephthalate soil release promoting polymer.
DETAILED DESCRIPTION OF TH~ INVENTION
.
The nonionic surfactants which are contemplated can
generally be any of the nonionics known to be useful as
detergents for cleaning soiled ~abrics.
Suitable nonionic surface active agents are
commercially available and are derived from the condensation o~
an alkylene oxide or equivalent reactant and a reactive-hydrogen
hydrophobe. The hydrophobic organic compounds may be aliphatic,
aromatic or heterocyclic, although the first two classes are
preferred. The preferred types of hydrophobes are higher
aliphatic alcohols and alkyl phenols, although others may be used
such as carboxylic acids, carboxamides, mercaptans,
sulphonamides, etc. The ethylene oxide condensates with higher-
alkyl phenols or higher fatty alcohols represent preferred
, 2~il716
classes of nonionic compounds. Usually, the hydrophobic moiety
should contain at least about 6 carbon atoms, and preferably at
least about 8 carbon atoms, and may contain as many as about 50
carbon atoms or more, a preferred range being from about 8 to 22
carbon atoms, especially from 10 to 18 carbons for the aliphatic
alcohols, and 12 to 20 carbons for the higher alkyl phenols. The
amount of alkylene oxide will vary considerably de~ending upon
the hydrophobe but as a general guide and rule, at least about 3
moles of alkylene oxide per mole of hydrophobe up to about 200
moles, preferably from about 3 to 50 moles, more preferably 5 to
20 moles of alkylene oxide per mole of hydrophobe will provide
the required cleaning performance and compatibility with the
other components.
Preferred classes of nonionic surfactants are
lS represented by the formulae
R0(CH2cH2O)nH (I)
wherein R is a primary or secondary alkyl chain of from
about 8 to 22 carbon atoms and n is an average of from
S to 50, preferably 5 to 20, especially 6 to 13;
20 and
Rl ~ o-(cH2cH2o)mH (II)
wherein Rl is a primary or secondary alkyl chain of
from 4 to 12 carbon atoms, and m is an average of 5 to
50, preferably 5 to 20, especially 6 to 13.
The preferred alcohols from which the compoUnds of
formula (I) are prepared include lauryl, myristyl, cetyl, stearyl
and oleyl and mixtures thereof. Especially preferred values of R
are Clo to Clg with the C12 to Cls alkyls and mixtures thereof
being especially preferred.
- 20~1716
The preferred values Of Rl in formula ~II) are from C6
to Cl2, with C8 and Cg, including octyl, isooctyl and nonyl being
especially preferred.
Typical examples of a nonionic compound of formula (I)
are lauryl alcohol condensed with 5 or 7 or ll moles ethylene
oxide. Typical examples of a nonionic compound of formula (II) .
are isooctyl phenol or nonyl phenol condensed with 3 to 8 moles
ethylene oxide.
Other nonionic compounds which may be used include the
polyoxyalkylene esters of the organic acids such as the higher
fatty acids, the rosin acids, tall oil acids, acids from
petroleum oxidation products, etc. These esters will usually
contain from about 10 to about 22 carbon atoms in the acid moiety
and from about 3 to about 30 moles of ethylene oxide or its
equi~alent.
Still other nonionic surfactants are the alkylene oxide
condensates with the higher fatty acid amides and amines. The
fatty acid group will generally contain from about 8 to about 22
carbon atoms and this will be condensed with about 3 to about 30
moles of ethylene oxide as the preferred illustration. The
corresponding carboxamides and sulphonamides may also be used as
substantial equivalents.
Although ethylene oxide has been exemplified as the
alkylene oxide group present in the nonionic surfactants, it is
also within the scope of the invention to use nonionic
surfactants formed with propylene oxide, preferably mixture of
ethylene oxide and propylene oxide. For example, the nonionic
surfactants sold under the well-known Plurafac series, such as
Plurafac B-26, the reaction product of a higher linear alcohol
and a mixture of ethylene and propylene oxides, containing a
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20l11716
mixed chain of ethylene oxide and propylene oxide, terminated by
a hydroxyl group.
In the preferred poly-lower alkoxylated higher
alkanols, to obtain the best balance of hydrophilic and
lipophilic moieties, the number of lower alkoxides will usually
be from 40% to 100~ of the number of carbon atoms in the higher
alcohol, preferably 40 to 60% thereof and the nonionic detergent
will preferably contain at least 50% of such preferred poly-lower
alkoxy higher alkanol. Higher molecular weight alkanols and
various other normally solid nonionic detergents and surface
active agents may be contributory to gelation of the liquid
detergent formulations and consequently, will preferably be
omitted or limited in quantity in the present liquid
compositions, although minor proportions thereof may be employed
for their cleaning properties, etc. With respect to both
preferred and less preferred nonionic detergents, the alkyl
groups present therein will most preferably be linear although a
minor degree of slight branching may be tolerated, such as at a
carbon next to or two carbons removed from the terminal carbon of
the straight chain and away from the ethoxy chain, if such
branched alkyl is no more than three carbons in length. Normally
the proportion of carbon atoms in such a branched configuration
will be minor, rarely exceeding 20% of the total carbon atom
content of the alkyl. Similarly, although linear alkyls which
are terminally joined to the ethylene oxide chains are highly
preferred and are considered to result in the best combination of
detergency, biodegradability and non-gelling characteristics,
medial or secondary joinder to the ethylene oxide in the chain
may occur. It is usually in only a minor proportion of such
alkyls, generally less than 50% but, as is in the case of, for
- 2~17~6
example, the Tergitols, may be greater. Also when propylene
oxide is present in the lower alkylene oxide chain, it will
usually be less than 20% thereof and preferably less than 10%
thereof, although higher percentages may also be used as in some
of the Plurafacs.
The amount of the nonionic will generally be the
minimum amount which when added to the wash water will provide
adequate cleaning performance. Generally, amounts ranging from
about 1 to about 50%, preferably from about 10 to about 40%, and
especially preferably from about 12 to 35% by weight of the
composition, can be used.
A second essential ingredien~ in the instant
formulations is the cationic fabric softener. Softening agents
are used to render fabrics or textiles soft, and the terms
"softening" and "softener" refer to the handle, hand, touch or
feel this is the tactile impression given by fabrics or textiles
to the hand or body and is of aesthetic and commercial
importance. The cationic fabric softeners used in the present
invention are the mono-higher alkyl quaternary ammonium compounds
represented by the following formula:
[R2 ~ = R3~ + (III)
wherein R2 is a long chain aliphatic radical having from 10 to 22
carbon atoms, and the three R3's are, independently, lower alkyl
or hydroxy alkyl radicals and X is a water-soluble, salt-forming
anion such as halide, i.e. chloride, bromide, iodide; sulfate;
citr~te, acetate; hydroxide; methosulfate; ethosulfate;
phosphate; or similar inorganic or organic solubilizing radical.
The carbon chain of the aliphatic radical containing 10 to 22
carbon atoms, especially 12 t~ 20, preferably 12 to 18, and
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especially preferably 16 to 18 carbon atoms, may be straight or
branched, and saturated or unsaturated. The lower alkyl radicals
have from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms,
especially preferably methyl, and may contain a hydroxyl radical.
Preferably, the long carbon chains are obtained from long chain
fatty acids, such as those derived from tallow and soybean oil.
The terms "soya" and "tallow", etc., as used herein refer to the
source from which the long chain fatty alkyl chains are derived.
Mixtures of the quaternary ammonium compound fabric softeners may
be used. The preferred ammonium salt is a mono-higher alkyl
trimethyl ammonium chloride wherein the alkyl group is derived
from tallow, hydrogenated tal-low or stearic acid. Specific
examples of quaternary ammonium softening agents of the formula
~III) uitable for use in the composition of the present invention
include the following: tallow trimethyl ammonium chloride,
hydrogenated tallow trimethyl ammonium chloride, trimethyl
stearyl ammonium chloride, triethyl stearyl ammonium chloride,
trimethyl cetyl ammonium chloride, soya trimethyl ammonium
chloride, stearyl dimethylethyl ammonium chloride, tallow-
diisopropylmethyl ammonium chloride, the corresponding sulfate,
methosulfate, ethosulfate, bromide and hydroxide salts thereof,
etc.
Another useful class of commercially available
quaternary ammonium fabric softener compounds are the ethoxylated
compounds of formula ~IV~:
~R2-~-(CH2c~20)~ X~ (IV)
~CH2CH2O)yH
wherein X, R2 and R3 are as defined for formula (III) and x and y
20 11716
are each positive numbers of at least 1 and the sum x + y is from
2 to 15.
An especially preferred compound of formula (IV) is
so:Ld by Armak under the trademark Ethoquad 18/12 (R3 = CH3-,
R2 = C18 alkyl, x + y = 2).
The amount of the monoalkyl quaternary cationic fabric
softener can generally range from about 1 to about 20%,
preferably from about 2 to about 16%, and especially preferably
from about 2 to 10~, by weight of the composition.
1~ The weight ratio of the nonionic surface active agent
to the cationic fabric softener can be within the range of from
about 1:1 to 15:1, preferably-from about 1.5:1 to 10:1,
especially preferably from about 2:1 to 8:1.
The anionic detergents which are contemplated can
generally be any of the anionics known to be useful in the
formulation of detergents for cleaning soiled fabrics.
The most preferred anionic detergent is a
sulfosuccinamate surfactant.
These compounds are characterized by having a 10 to 22
open chain hydrocarbon substituent bonded to the nitrogen atom of
the carbonamide (-CON = ) group present at one carboxy terminal
end group of the succinamate moiety, and by the sulfonyl (-SO3-)
group bonded to one of the carbon atoms at the alpha- or beta-
position with respect to the carbonamide group.
Examples of the sulfosuccinamate compound include
disodium N-octadecyl sulfosuccinamate (available as Alkasurf SS-
TA from Alkaril Chemicals, or as ASTROMID 18 from Alco Chemical
Corp.), disodium N-oleyl sulfosuccinamate (available from Alkaril
Chemicals as Alkasurf SS-OA); tetrasodium N-(1,2-
dicarboxyethyl)N-octadecyl sulfosuccinamate (available as
~ 17~6
ASTROMID 22 from Alco Chemical Corp., as Monawet SNO-35 from Mona
Industries, Inc. or Aerosol 22 from American Cyanamid Corp.).
More generally, however, suitable sulfosuccinamate
compounds can be represented by the following general formula
5 (V):
O
" R4
CH2-C-N-- (V~
Z-O3S-CH-COOZ
where Z is a monovalent salt-forming cation, such as
alkali metal, ammonium and amine,
R4 is hydrogen, lower alkyl, carboxy(lower alkyl), or
1,2-dicarboxy(lower alkyl), and
R5 is an open chain hydrocarbon of from 10 to 22 carbon
atoms.
As the alkali metal sodium potassium, or lithium are
pre~erred and sodium is especially preferred.
The monovalent amine salt forming cation may be, Eor
example, a mono-, di-, or tri-lower alkanolamine, such as mono-,
di-, or triethanolamine.
The "lower alkyl" group can have from 1 to 5,
preferably 1 to 3, especially preferably 1 to 2 carbon atoms.
The open chain hydrocarbon for R5 may be saturated or
unsaturated, and may be a straight chain or branched chain group,
preferably an alkyl or alkenyl of from 14 to 18, especially 16 to
18 carbon atoms, such as, for example, tallow, hydrogenated
tallow, fractionated tallow, oleyl, octadecyl, stearyl, etc.
When R4 is carboxy~lower alkyl) or 1,2-dicarboxy(lower
alkyl~, such as carboxyethyl, carboxypropyl, carboxy-2-methyl-
ethyl, 1,2-dicarboxyethyl, etc., ~he carboxyl group or groups may
. . ~'
. . -
20~1716
¦ be in the form -COOY where Y is the group z or lower alkyl;
¦ preferably Y is Z, especially preferably sodium.
¦ The amount of the sulfosuccinamate must be carefully
¦ selected depending on such factors as the nature and amount of
¦ the nonionic surfactant and cationic fabric softener, the
particular sulfosuccinamate, as well as the anticipated washing
¦ conditions, including, for example, type of fabrics, soils, wash
¦ temperature, water hardness, etc. Generally, however, best
¦ cleaning performance has been achieved when the amounts of
¦ sulfosuccinamate surfactant, nonionic surfactant and mono-higher
¦ alkyl cationic fabric softener are each in the following ranges -
¦ in parts by weight based on the total composition:
¦ Broad Preferred
¦ ~a) Nonionic surfactant 10-50 12-35
15 ¦ (b) Monoalkyl quaternary 1-20 2-16
¦ ~c) Sulfosuccinamate surfactant 1-20 2-16
¦ Within the above ranges the weight ratios of (a):(b), (a):(c) and
(b):(c) are also important, although again, the optimum values
may differ for different compounds and different washing
conditions. For most cases, however, the ratios (a):(b) and
(a):~c) are in the range of from about 15:1 to 1:1, preferably
10:1 to 1.5:1, especially preferably 8:1 to 2:1. The weight
ratio of (b):(c) should generally be within the range of from
about 3:1 to 1:3, preferably from about 2:1 to 1 2, especially
preferably from about 1.3:1 to 1:2. further, the weigh ratio of
(a):(b)~(c) is from about 10:1 to 1:1, preferably 6:1 to 1.5:1.
For example, in accordance with one preferred
embodiment of the invention wherein the nonionic is a C12-Cls
alcohol ethoxylated with an average of 7 moles ethylene oxide per
20~1716
mole of alcohol, ~such as the Shell Oil Co. product Neodol 25-7)
in an amount of from about 15 to 25% by weight of the total
composition, the monoalkyl quaternary fabric softener is tallow
trimethyl ammonium chloride, and the sulfosuccinamate is
tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate
(e.g. Monawet SW0-35) the preferred ratios of the nonionic to
quaternary and quaternary to the sulfosuccinamate are in the
range of from about 12:1 to 4:1 and from about 1:1 to 1:2,
respectively, under typical washing conditions, e.g. 120~F, 0.2
product concentration, 100 ppm hardness ions, for a broad range
of fabrics and soils.
Other anionic detergents may be utilized in the present
invention, in lieu of the sulfosuccinamate surfactant, but in a
particularly preferred embodiment of the invention the
sulfosuccinamate surfactant is utilized in conjunction with an
anionic surfactant.
¦ Thus, as disclosed in the Applicant's aforementioned
¦ copending application Serial No. 661,775, the softening and anti-
¦ static performance of the mixture of nonionic surfactant and
¦ mono-higher alkyl quaternary ammonium compound fabric softening
¦ agent is significantly enhanced by the use of a linear alkyl
aromatic sulfonate surfactant, preferably as a 1:1 molar complex
with the quaternary fabric softener.
Examples of suitable anionic surfactants include the
water-soluble salts, e.g. the sodium, potassium, ammonium,
alkylolammonium salts of higher linear alkyl aromatic sulfonates
containing about 8 to 26 carbon atoms, preferably 10 to 22 carbon
atoms, in the alkyl radical. (The term alkyl includes the alkyl
portion of the higher acyl radicals.)
~ ~0~1716
Preferred examples of the linear alkyl aromatic
s~lfonates are those containing from 10 to 16 carbon atoms in the
line3r alkyl radical, e.g., the sodium, potassium, and ammonium
salts of higher linear alkyl benzene sulfonates, higher linear
alkyl toluene sulfonates, higher linear alkyl phenol sulfonates,
and higher linear alkyl naphthalene sulfonates. The linear
higher alkyl benzene sulfonates such as the C10-C16 alkyl,
especially Clo-C14 alkyl, for example C12 ~n-dodecyl) alkyl
benzene sulfonates, are especially preferred anionic surfactants.
In addition to the linear alkyl aromatic sulfonates
another preferred class of anionic surfactants which can enhance
the overall performance, especially anti-static and softening, of
the invention detergent compositions include the alkyl ether
sulfates of formula R6O(CH2CH20)p-SO3M,
where R6 is higher alkyl having from 8 to 20,
especially 10 to 18, carbon atoms,
M is a solubilizing salt-forming cation, such as an
alkali metal ion, alkaline earth metal ion, ammonium ion,
ammonium ion substituted with from 1 to 3 lower alkyls, or mono-,
di- and tri-alkanolamines having 2 to 3 carbon atoms in the
alkanol group or groups, and p is a number of from 2 to 8,
preferably 2 to 6 (especially from 1/5 to 1/3 or 1/2 the number
of carbon atoms in R6). A preferred polyethoxylated alcohol
.. ... . . ~
~ suifate surfactant is available from Shell Chemical Company and
is marketed as Neodol 25-3S. This material, the sodium salt, is
normally sold as a 60% active ingredient product in an aqueous
solvent medium. Although Neodol 25-3S is the sodium salt, the
potassium salt and other suitable soluble salts of the
triethenoxy higher alcohol (12 to 15 carbon atoms) sulfate and
other such compounds herein described, such as have already been
20~171~
referred to and those described below, may also be used in
partial or complete substitution for the sodium salts. As with
the various materials of the present compositions, mixtures
thereof may be utili~ed.
~xamples of the higher alcohol polyethenoxy sulfates
which may be employed as the anionic surfactant constituent of
the present liquid detergents or as partial substitutes for this
include: mixed C12_15 normal or primary alkyl triethenoxy
sulfate, sodium salt; myristyl triethenoxy sulfate, potassium
salt; n-decyl diethenoxy sulfate, diethanolamine salt; lauryl
diethenoxy sulfate, ammonium salt; palmityl tetraethenoxy
sulfate, sodium salt; mixed C14_15 normal primary alkyl mixed
tri- and tetraethenoxy sulfate, sodium salt; stearyl
pentaethenoxy sulfate, trimethylamine salt; and mixed ClO_lg
normal primary alkyl triethenoxy sulfate, potassium salt. Minor
proportions of the corresponding branched chain and medially
alkoxylated detergents, such as those described above but
modified to have the ethoxylation at a medial carbon atom, e.g.
one located four carbons from the end of the chain, may be
employed and the carbon atom content of the higher alkyl will be
the same. Similarly, the joinder to the normal alkyl may be at a
secondary carbon one or two carbon atoms removed Erom the end o~
the chain. In either case, as previously indicated, only minor
proportions should be present, such as 10 or 20%, in the usual
case.
As is the case with the preferred nonionic detergents,
the present poly-lower alkoxy higher alkanol sulfates are
readily biodegradable and of better detergency when the fatty
alkyl is terminally joined to the poly(lower oxyalkylene) chain,
which is terminally joined to the sulfate. Again, as in the
20~171~
case of the nonionic detergents, a small proportion, for example,
not more than 10%, of branching, and medial joinder are
to:Lerable. Generally, it will be preferred for the alkyl in the
anionic alkoxylate surfactant as in the nonionic detergent to be
a mixture of different chain lengths, as 11, 12, 13, 14 and 15
carbon atoms or 12 and 13 carbon atom chains, rather than all of
one chain length. Nevertheless, the invention is applicable to
liguid detergents containing pure nonionic and anionic
components.
Of course, ethylene oxide is the preferred lower
alkylene oxide of the anionic alkoxylate surfactant, as it is
with the nonionic detergent, and the proportion thereof in the
polyethoxylated higher alkanol sulfate is preferably 2 to 5 mols
of ethylene oxide groups present per mol of anionic surfactant
and in more preferred compositions from 2 to 4 mols will be
present, with three mols being most preferred, especially when
the higher alkanol is of 12 to 13 carbon atoms or 11 or 12 to 15
carbon atoms. To maintain the desired hydrophile-lipophile
balance, when the carbon atom content of the alkyl chain is in
the lower portion of the 10 to 18 carbon atom range, the ethylene
oxide content of the detergent may be reduced to about two mols
per mol; whereas, when the higher alkanol is of 16 to 18 carbon
atoms, in the higher part of the range, the number of ethylene
oxide groups may be increased to 4 or 5 and in some cases to as
high as 8 or 9. Similarly, the salt-forming cation may be
altered to obtain the best solubility. It may be any suitable
solubilizing metal or radical but will most frequently be alkali
metal, e.g. sodium, or ammonium. If lower al~ylamine or
alkanolamine groups are utilized, the alkyls and alkanols will
usually contain from 1 to 4 carbon atoms and the amines and
20~1716
alkanolamines may be mono-, di- and tri-substituted, as in
monoethanolamine, diisopropanolamine and trimethylamine.
The poly-lower alkoxy higher alkanol sulfates and the
linear alkyl aromatic sulfonates, are highly preferred anionic
surfactants in the present compositions but other anionic
surfactants may be employed with them or in place of such
compounds. Particularly, alpha-olefin sulfonates, paraffin
sulfonates and higher alcohol sulfates may be used. ~he olefin
sulfonate salts generally contain long chain alkenyl sulfonates
or long chain hydroxyalkane sulfonates (with the O~ being on the
carbon atom which is not directly attached to the carbon atom
bearing the -SO3H group). The olefin sulfonate detergent usually
comprises a mixture of such types of compounds in varying
amounts, often together with long chain disulfonates or sulfate-
sulfonates. Such olefin sulfonates are described in many
patents, such as U.S. Patent Nos. 2,061,618; 3,409,637;
3,332,880; 3,420,875; 3,428,654; 3,506,580 and British Patent No.
1,129,158. The number of carbon atoms in the olefin sulfonate is
usually within the range of 10 to 25, more commonly 10 to 20, or
12 to 18, e.g. a mixture principally of C12~ C14 and C16~ having
an average of about 14 carbon atoms, or a mixture principally of
C14, C16 and Clg, having an average of about 16 carbon atoms.
Another class of useful anionic surfactant is that of
the higher paraffin sulfonates. These may be primary or
secondary paraffin sulfonates made by reacting long chain alpha-
olefins and bisulfites, e.g. sodium bisulfite, or paraf~in
sulfonates having the sulfonate groups distributed along the
paraffin chain, such as the products made by reacting a long
chain paraffin with sulfur dioxide and oxygen under ultraviolet
light, followed by neutralization with sodium hydroxide or other
2D~1716
suitable base (as in U.S. Patents 2,503,280; 2,507,088;
31260,741; 3,372,188, and German Patent 735,096). The paraffin
sulfonates preferably contain from 13 to 17 carbon atoms and
will normally be the monosulfonate but if desired, may be di-,
5 tri- or higher sulfonates. Typically, the di- and poly-
sulfonates will be employed in admixture with a corresponding
monosulfonate, for example, as a mixture of mono- and
di-sulfonates containing up to about ~0% of the disulfonate. The
hydrocarbon substituent thereof will preferably be linear but if
10 desired, branched chain paraffin sulfonates can be employed,
although they are not as good with respect to biodegradability.
The paraffin sulfonate may be terminally sulfonated or the
sulfonate substituent may be joined to the 2-carbon or other
carbon atom oE the chain and, similarly, any di- or higher
15 sulfonate employed may have the sulfonate groups distributed over
different carbons of the hydrocarbon chain.
The paraffin sulfonates and olefin sulfonates are used
in the form of their alkali metal, e.g. sodium and potassium,
ammonium, or mono-, di-, and tri-loweralkanol-amine salts, or
20 mixtures thereof. Triethanolamine is the preferred alkanolamine
salt forming cation. The linear alkylbenzene sulfonates and
alkyl ether sulfates aee especially preferred as the anionic
surfactant.
These anionic surfactants can not only in~eract with
25 the mono-higher alkyl quaternary compound to improve softening
and anti-static performance but also function to cause various
additional optional detergent adjuvants, as described in detail
more fully below, especially optical brighteners, to deposit more
effectively on the fabrics being laundered.
20~17 i 6
Although no specific rules can be applied for every
combination of ingredients and for all washing conditions, it has
been observed as a general rule that as between the two preferred
classes of anionic surfactants, the linear alkyl benzene
sulfonates are usually slightly more e~fec~ive than the alkyl
ether sulfates in terms of softening performance but slightly
inferior in terms of cleaning performance - although the addition
of any anionic surfactant often provides only slight improvements
in cleaning performance as compared to the same composition
without anionic surfactant. Naturally mixtures of two or more of
the anionic surfactants can be used.
Since the anionic surfactant presumably forms a complex
with the cationic softener to provide the enhanced
softening/anti-static performance without interfering with, or
slightly improving, the cleaning performance of the nonionic or
with the brightener, in the detergent formula, the ratio of
cationic to anionic is particularly critical since large excesses
of either component could interfere with overall performance.
Accordingly, ratios of cationic to anionic of from about 1.3:1 to
1:1.5, preferably 1.2:1 to 1:1.2, especially preferably 1.1:1 to
1:1.1 and most preferably about 1:1 will provide improved
softening performance and anti-static performance, as well as
improved whitening and perhaps cleaning.
The total amount of the cationic/anionic softener
mixture in the composition generally will range from about 2 to
20%, preferably 5 to 15%, by weight based on the total
composition. Moreover, the total amount of cationic softener and
anionic surfactant will generally be in the range of from about
20 to 100%, preferably 30 to 80%, by weight, based on the
nonionic surfactant. Furthermore, within the above amounts and
20!11'71~
ratios, the cationic/anionic softener mixture will be compatible
with the nonionic surfactant, sulfosuccinamate and the optical .
brighteller, etc.
In any event, the total amount of anionic detergent
should be within the range of 1 to 30~ by weight of the total
composition, preferably, 2 to 26% by weight. Preferably, the .
anionic detergent comprises a sulfosuccinamate compound and an
anionic surfactant selected from the group consisting of linear
higher alkyl aromatic sulfonate, poly(lower alkoxy)higher alkanol
sulfonate, olefin sulfonate and paraffin sulfonate with the
sulfosuccinamate compound being present in an amount of 2 to 20
by weight of the total composition and the anionic surfactant
being present in an amount of up to 10~ by weight of the total
composition. Most preferably, the weight ratio of the cationic .
fabric softener-anti-static agent to the sulfosuccinamide
compound is in the range of from about 3:1 to 1:3; and the weight
ratio of the cationic fabric softener-anti-static agent to said
anionic surfactant selected from the group consisting of linear
higher alkyl aromatic sulfonate, poly(lower alkoxy)higher alkanol
sulfonate, olefin sulfonate and paraffin sulfonate is in the
range of from about 1.3:1 to 1:1.5. Additionally, it is .
preferred that the weight ratio of the sulfosuccinamate compound
to the anionic surfactant selected from the group consisting of
linear higher alkyl aromatic sulfonate, poly(lower alkoxy)higher
alkanol sulfonate, olefin sulfonate and paraffin sulfonate is in
the range of from about 1.3:1 to about 1:1.5, most preferably,
about 1.2:1 to 1:1.2.
The soil release promoting polymer which as a water-
soluble fraction is an essential component of the compositions of
this invention is a polymer of polyethylene terephthalate and
20-~1716
polyoxyethylene terephthalate which is dispersible in water and
is depositable from wash water containing nonionic detergent onto
synthetic organic polymeric fibrous materials, especially
polyesters and polyester blends, so as to impart soil release
properties to them, while maintaining them comfortable to a
wearer and not preventing or significantly inhibiting vapor
transmission through them. Such polymers have also been found to
possess anti-redeposition properties. They tend to maintain
soil, such as oily soil, dispersed in wash water during washing
and rinsing, so that it is not redeposited on the laundry.
Useful products are copolymers of ethylene glycol or another
suitable source of ethylene oxide moiety, such as polyoxyethylene
glycol and terephthalic acid or a suitable source of the
terephthalic moiety. The copolymers may also be considered to be
lS condensation products of polyethylene terephthalate, sometimes
referred to as ethylene terephthalate polymer, and
polyoxyethylene terephthalate. While the terephthalate moiety is
preferred as the sole dibasic acid moiety in the polymer, it is
within the scope of the invention to utilize relatively small
proportions of isophthalic acid and/or orthophthalic acid (and
sometimes other dibasic acids) to modify the properties of the
polymer. However, the proportions of such acids will normally be
less than 10% of the phthalic moieties present in the final
polymer, and, preferably, less than 5%.
The weight average molecular weight of the polymer may
be as low as 8,000 or as high as 60,000. In the polymers
util~zed the polyoxyethylene will be of a molecular weight in the
range of about 500 to 10,000 preferably about 2,500 to 5,000,
more preferably 3,000 to 4,000. In such polymers, the molar
ratio of polyethylene terephthalate units (A)
1 2041716
t OCH2C~2O C- ~ -C ~ ~A)
l to polyoxyethylene terephthalate units (B)
~ ~ oc~2cH2 )n O C - ~ C ~ (B)
will be within the range of 2:1 to 6:1, preferably 5:2 to S:l,
¦ most preferably 3:1 to 4:1. The proportion of ethylene oxide to
¦ phthalic moiety in the polymer will be at least 10:1, preferably
¦ 20:1 or more, and most preferably within the range of 20:1 to
30:1.
¦ Although suitable methods for making these polymers are
¦ described in the literature, such polymers may be considered as
¦ having been randomly constructed from polyethylene terephthalate
¦ and polyoxyethylene terephthalate moieties such as may be
¦ obtained by reacting polyethylene terephthalate (e.g., spinning-
¦ grade) and polyoxyethylene terephthalate or reacting the ethylene
¦ and polyoxyethylene glycols and acid (or acid precursor) thereof.
20 ¦ The described materials are available from various
sources. Useful copolymers for the manufacture of the water-
soluble fraction of the present invention are marketed by Alkaril
Chemicals, Inc. and commercial products of such company are sold
by them under the trademarks Alkaril QCJ and Alkaril QCF.
Products available from them in limited quantities, designated
2056-34B and 2056-41 have also been found to be useful. The QCJ
product, normally supplied as an aqueous dispersion (about 15~
solidl~ is also available as an essentially dry solid, i.e. the
QCF product. When it is anhydrous or low in moisture content
(less than about 2~ moisture), it looks like a light brown wax in
which the molar ratio of ethylene oxide to phthalic moiety is
2~1716
about 22~ n a 16~ dispe~sion, the viscosity at 100F is about
96 centistokes. The 2056-~1 polymer is like a hard, light brown
wax and the ethylene oxide to phthalic moiety ratio is about 16
to 1, with the viscosity, under the same condi~ions as previously
mentioned, being about 265 centistokes. The 2056-34B polymer
appears to be a hard, brown wax in which the molar ratio of
ethylene oxide to phthalic moiety is about 10.9 to 1, and its
viscosity, under the same conditions as previously mentioned, is
about 255 centistokes. The QCJ/QCF polymers have melting points
(differential thermal analysis) of about 50-60C, a carboxyl
analysis of 5 to 30 equivalents/106 grams, and a pH of 6-8 in
distilled water at 5 weight ~ concentration.
In order to produce the water-soluble fraction of the
polymer utilized in the present invention, the above-noted
polymers are subjected to a cold filtration process while in
aqueous dispersion.
This cold filtration process separates a "water-
insoluble" fraction as a precipitate which is rich in
polyethylene terephthalate and exhibits little or no soil release
activity. The filtrate contains a "water-soluble" fraction which
exhibits soil release activity and is rich in polyoxyethylene
terephthalate. The filtrate may be further separated into actlve
fractions by extraction with an organic solvent, e.g., a polar
organic solvent such as an alkyl halide, especially a lower alkyl
halide, e.g., methylene chloride.
In particular, a 5-10% by weight aqueous dispersion of
the polyethylene terephthalate-polyoxyethylene terephthalate
polymer is chilled to less than 40F and then filtered to recover
insoluble material. The filtrate, so-produced, constitutes the
"water-soluble" fraction of a polyethylene terephthalate-
~}
2~171 b'
polyoxyethylene terephthalate soil release promoting polymer used
in the present invention. This "water-soluble" fraction may be
further extracted with an alkyl halide solvent, such as methylene
chloride, to form two sub-fractions either of which may be used
in lieu of the total "water-soluble" fraction.
As will be readily recognized, filtration may be
replaced by any other technique suitable for solid-liquid
separation, e.g., decantation, centrifugation, etc. Likewise,
the "water-soluble" fraction may be recovered by drying of the
dispersion(s).
The liquid carrier for the instant liquid detergent
composition is preferably an aqueous one, and may be water alone
or may be substantially water with additional solvents added for
solubilizing particular ingredients, as is well known in the art.
Because of the availability of water and its minimum cost, it is
preferred to use water as the major solvent present. Yet,
amounts of other solvents, generally up to 20%, and preferably a
maximum of lS~ of the total content, may be used. Generally,
such a supplementing solvent will be either a lower alkanol or a
lower diol or polyol, e.g. ethanol, isopropanol, ethylene glycol,
propylene glycol, glycerol, or the like. Etheric polyols such as
diethylene glycol and those known as cellosolves may also be
used.
In addition to the supplemental solvent, it is also
generally preferred to include a hydrotropic material in the
formulation to maximize the compatibility of all of the active
ingr~dients and to make the liquid formulation more homogeneous
and stable. Examples of suitable hydrotropes include the alkali
metal aryl sulfonates, such as sodium benzene sulfonate, sodium
toluene sulfonate, sodium xylene sulfonate, and the corresponding
. 2041716
potassium salts. The hydrotrope can be used in amounts up to
about 15%, preferably ~p to 10~ by weight of the total
composition, for example, 1 to 8%, or 2 to 6%. Although the
aqueous carriers are preferred, non-aqueous liquid carriers, s~ch
as the organic cosolvents mentioned above, may be used as the
sole or major liquid carrier, i.e. the non-aqueous liquid
carriers may comprise from about 50 to 100% by weight of the
liquid carrier, the balance, if any, constituting water and/or
hydrotropic material. Mixtures oE two or more organic solvents
may also be used.
Various selected compatible adjuvants may also be
present in the detergent composition to give it additional
desired properties, either of functional or aesthetic nature.
Thus, there may be include~ in the formulation: enzymes, e.g.
proteases, amylases, lipases, etc., and mixtures thereof;
bleaching agents; bleach activators and stabilizers; soil-
suspending or anti-redeposition agents, e.g. polyvinyl alcohol,
sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose;
dyes, bluing agents, pigments, optical brighteners, e.g., cotton,
amide and polyester brighteners; bactericides, e.g.
hexachlorophene; preservatives, e.g. methyl parasept or sodium
benzoate; ultraviolet absorbers; p~ modifying agents, e.g.
amines, pH buEfers; opaciEying agents, e.g. behenic acid,
polystyrene suspensions, etc.; and perfumes. The adjuvants, of
course, will be chosen to be compatible with the main
constituents of the deter~ent formulation.
t f the adjuvants mentioned perhaps the most important
for functional effect are the optical brighteners because the
modern housewife has come to expect that washed clothing will no
longer merely be clean and white but will also be bright in
20 11716
appearance. The optical brighteners are substantive to textiles
being washed (such substantivity may be selective) and sometimes
are of comparatively low solubilities. Accordingly, it is
important that they be maintained in solution in the liquid
detergent composition and, even more important, they must be
immediately dispersed in the wash water so as to avoid producing
a wash containing noticeable brightened spots, rather than a
uniformly bright appearance. Here, the choice of brightener to
obtain best results will be ascertainable to one of skill in the
art. It has been found that relatively small quantities of
brighteners should be used, so as not to exceed the limits of
solubilities. Also, within the class of these materials certain
brighteners have been found to be especially readily dissolved,
and thus are suitable for incorporation in these products.
Fortunately, such preferred brighteners include both cotton and
amide-polyester-brighteners, making them suitable for use with
laundries containing a variety of material and synthetic
materials. Among the commercial brighteners that are used in the
present system are Tinopal UNP~, Tinopal css, Tinopal 5sM ~Ciba-
Geigy), Arctic White CC, Artic White CWD (Hilton Davis), and the
following Phorwhites from Verona: BHC, BKL, BUP, BBH solution
BRV solution, DCR liquid, DCBVF, EV liquid, DBS liquids and ANR.
Other types of optical brighteners which give superior
whitening effects are those components having no sulfonate
moieties. The preferred class of brighteners for use in the
present invention include the 2-(4-styrylphenyl)-2H-naphtholll,2-
dl tr~azoles, 4,4'-bis(1,2,3-triazol-2-yl)stilbenes, 4,4'-
bis(styryl) bisphenyls, and the y-aminocoumarins. Specific
e~amples of these brighteners include 4-methyl-7-diethylamino
coumarin, 1,2-bls~benzimidazol-2-yl)ethylene, and the 1,3-
~i~
2Q~1716
diphenyl-phrazolines, as well as 2,5-bis(benzoxazol-2-yl~
thiophene, 2-styryl-naphth ~1,2-d] oxazole, and 2-(stilben-4-yl)-
2H-naphtho[1,2-d)triazole.
The optical brightener content of the liquid
composition will normally be from about 0.2% to about 3.0%, and
preferably from 0.25 to 2~7%. Such concentrations are soluble in
the described liquid detergents and are effective in noticeably
brightening the washed clothing. As mentioned above, the
presence of the anionic surfactant can enhance the uniform
deposition of the optical brightener.
The contents of the other adjuvants is preferably
maintained at less than 5%, preferably less than 3%, by weight of
the product. Use of more than the described proportions of the
such compounds can often significantly change the properties,
e.g. stability, of the liquid detergent, and therefore should be
avoided.
Although the liquid detergent softener composition of
the present invention is a stable, clear one-phase liquid, a
compatible opacifying agent may be added to impart a creamy
appearance to the formulation.
Still another optional but highly preferred ingredient
in the present detergent compositions is an ethoxylated fatty
amine, such as the Ethomeen0 series of compounds of ~rmak
Company and the Varonic~ series from Ashland Chemicals. These
compounds can be represented by the general formula
R7 N (CH2CH2O)XH
t (C~2CH2O)yH
where R7 i5 a fatty alkyl group of from about 10 to 22,
preferably 12 to 18, carbon atoms and the sum of x + y is from
about 2 to about 15. The R7 group may be saturated or
20!1171~
unsaturated, and, for example, may be derived from coco fatty
acid, oleic acid, soya fatty acid, tallow fatty acid, stearic
acid, or mixtures of these acids.
The ethoxylated amines contribute to impro~e cieanirly,
softening and static control. Usually amounts of the
ethoxylated amine up to about 15~, preferably up to about 10%,
for example 1-10~, or 1-8%, especially 2~8%, by weight of the
total liquid composition are satisfactory.
To assist in solubilizing the detergents and optical
brighteners which may be present in the liquid detergents a small
proportion of alkaline material or a mixture of such materials is
often included in the present formulations. Suitable alkaline
materials include mono-, di- and trialkanolamines, alkyl amines,
ammonium hydroxide and alkali metal hydroxies. Of these, the
preferred materials are the alkanolamines, preferably the
trialkanolamines and of these, especially triethanolamine. The
pH o the final liquid detergent, containing such a basic materia
will usually be neutral or slightly basic. Satisfactory pH
ranges are fro~ 7 to 10, preferably about 7.5 to 9.5, but because
of pH reading of the liquid detergent, using a glass electrode
and a reference calomel electrode, may be inaccurate, due to the
detergent system often being essentially non-aqueous, a better
indication is obtained by measuring the pH of a 1% solution of
the liquid detergent in water. Such a pH will also normally be
in the range of about 7 to 10, preferably 7.5 to 9.5. In the
wash water, the pH will usually be in this range or might be
sligh~tly more acidic, as by 0.5 to 1 pH unit, due to the organic
acid content of soiled laundry. For the liquid formulations, the
viscosity at 25C will be in the range of 40 to 1000 centipoises,
preferably from 40 to 500 centipoises, according to measurements
20~171fi
that are made with a Brookfield viscosimeter at room temperaturev
suing a No. 1 spindle at 12 revolutions per minute.
The liquid composition is usually added to wash water
in an automatic washing machine of either the top loading GL
front loading type so that the concentration thereof in the wash
water may range from about 0.05 to 1.5~, usually 0.1 to 1.2~.
Generally, depending on the type of machine and the degree of .:
loading with the soiled fabrics, the amount of the liquid
formulation to be added will range from about 1/4 cup to about 1
1/4 cup, with the typical amount being about 1/2 cup (120
milliliters).
The wash water used may be a fairly soft water or water
of reasonable hardness, and will generally and preerably be used
at elevated temperature, especially at about 100F or higher,
lS such as 120F to 180F or higher. The composition of the present
invention is also useful in laundering clothes in very hard
waters and at lower temperatures. Thus, water hardness may range
from 0 to over 300 parts per million calculated as calcium
carbonate, and washing temperatures may be from 40 to 120F or
higher. Washing will be effected in an automatic washing machine
in which the washing is followed by rinsing and spin or other
draining or wringing cycles or operations. Of course, the
detergent composition may also be used for hand washing of
laundry, in which case it may sometimes be used full strength on
certain strains on the laundry, or the laundry may be soaked in a
higher concentration solution of detergent before washing.
~ The washing operations will generally take from three
minutes to one hour, depending on the fabrics being washed and
the degrees of soiling observed. After co~pletion of washing and
the spinning, draining or wringing operations, it is preferred to
2041716
dry the laundry in an automatic dryer soon thereafter but line
drying may also be employed.
The present deteryent-softener composition dissolves
very easily whether the wash water is warm or cold, and very
effectively cleans, softens and eliminates static charge on
clothing and other items of laundry without imparting a water
repellant finish thereto. It may be used in either top loading
or front loading washing machines and may be desirably adjusted
to foam to the correct extent. The product ls an attractive
clear, stable liquid which maintains its activity and uniformity
over a long shelf life. In tests in which the effects of using
it are compared to those from the employment of commercial liquid
laundry detergents, it rated very favorably.
This product may be prepared by simply admixing the
various ingredients at room temperature with agitation to ensure
solubilization thereof in the aqueous medium. The order of
addition of ingredients and the temperature of compounding may be
varied without adversely affecting the formation oE the single
phase, clear liquid product of instant invention.
The detergent-softener composition of the present
invention exhibits many desirable characteristics with regard to
both physical properties and performance in use. As to its
physical properties, the liquid compositions are pourable and
free-flowing from the container as manufactured and after aging.
They exhibit a high degree of stability upon storage at normal
room temperature of the order of about 70F over a period of many
monthts without any appreciable precipitation. As a result, the
consumer can utilize them conventionally by addition of very
small portions to a laundering bath, and the detergent and
softener will be present in constant composition in each portion.
2011716
While compatible adjuvant materials may be added to render the
final product translucent or opaque as desired, the requirement
for a one phase solution of the main ingredients insures that
effective washing and softening power will be obtained with each
portion and promotes the stability and homogeneity of the
product. The composition may be packaged in any suitable
container or packaging material such as metal, plastic or glass.
The following specific examples illustrate various
embodiments of the present invention. It is to be understood,
however, that such examples are presented for purpose of
illustration only, and the present invention is in no way to be
deemed as limited thereby.
EXAMPLE 1 - Preparation of Water-Soluble Fraction of Polyethylene
Terephthalate-Polyoxyethylene Terep thalate Polymer
10.0 grams of Alkaril QCF (Alkaril Chemicals, Inc.) was
dissolved/dispersed in 120 ml of water at 95C with stirring for
five minutes. The dispersion/solution was chilled to near
freezing and then f iltered to recover 2.2 grams of insoluble
material (Fraction 1). The filtrate was extracted with methylene
chloride and then the extract was evaporated to recover 3.5 grams
of a second solid (Fraction 2). The remaining aqueous
dispersion/solution was then evaporated to dryness and 3.0 grams
of a third solid (Fraction 3) was recovered. Each of the
fractions was characterized as set forth in the following Table
1.
1 40
20 il716
Table 1
Fraction 1Fraction 2 Fraction 3
Relative Amount of
Recovered Solids % 25 40 35 .
Water Soluble NO YES YES
CH2C12 Extractable - YES NO
Melting Point (C)96-150 47-51 45-52
Infra-Red Ratio
of Ether to Ester 1.4 4.0 2.6
ESCA Ratio of Ether
Carbons to Aromatic
Carbons 1.6 16 - .
Soil Release (~) 4 92 95
Example~2 - Preparation of an Aqueous Laundry Detergent
Composition
The following ingredients were mixed to form an aqueous .
laundry detergent composition:
Active Ingredient (~)
C12_15 Alcohol-7 Ethylene Oxide
(Neodol 25-7, Shell) 21
Tallow Trimethyl Ammonium Chloride
(Arguad T-50, Armak) 4
Linear Dodecyl Benzene Sulfonate 4 .
N- (1,2-Dicarboxyethyl)
N-AlkYl (C18)
Sulfosuccinamate, Tetrasodium
(Monawet SNO, Mona) 4
Sodium Xylene Sulfonate 4
"Water-Soluble" QCF
(Fraction #3, Example 1)
Wate~ (and incidental impurities) QS
The liquid was clear initially and remained clear after storage
for 1 week at 110F.
In contrast, when QCF (i.e. untreated QCF) is utilized
20~1716
in lieu of the water-soluble fraction, a fine precipitate settles
out on aging within 1 day at 110F.
Exarnple 3 - Dirty Motor Oil Release Tests
Clean swatches of varlous types were washed in a
standard automatic washing machine of the top loading type,
having a washing drum of 17 U.S. gallons capacity. After
addition of the swatches in a standard wash load of about eight
pounds, sufficient liquid detergent composition was added to the
wash water to provide a detergent composition concentration of
0.22% by weight, the wash water being of about 100 ppm hardness,
as calcium carbonate, and having a temperature of 120F. Two
swatches were employed for each of three different fabrics, i.e.
single knit Dacron~, double knit Dacron~, and Dacron~/cotton
blend (65/35~. The fabrics were washed using a normal wash cycle
for the washing machine, including rinsing, and subsequently the
swatches were dried.
After drying, the swatches were soiled in the center
thereof with equal volumes (about three drops) of used dirty
motor oil and then they were rewashed with the same detergent
composition. ~hiteness readings (Rd Values) of the stained areas
of the swatches were taken, using a reflectometer. Because such
readings represent whiteness and the used motor oil was black,
the readings were directly proportional to effectiveness of the
soil release promoting action of the detergent containing the
polyethylene terephthalate-polyoxyethylene terephthalate
copolymer or fraction thereof. The same test was r un on
contrbls, in which the swatches were first washed in the
detergent composition minus the polyethylene terephthalate-
polyoxyethylene tere2hthalate copolymer, subsequently, stained
witl the dirty motor oil, and then rewash wit~ the rame cor~trol ~
compos ion. Tests were conducted on freshly prepared deterg nt
cornpositions (initial) and aged detergent compositions (1 wk at
110F). The results are set forth in Table 2.
Table 2
5 Composition ¦ Rd Value
_ _ .
Dacron Dacron Dacron/
Sinqle Knit Double Knit Cotton
I Initial¦ Aged Initial _ Initial _ _ .
A~l) 87.0 85.8 85.0 85.4 80.9 80.5
B(2) 87.1 80.1 85.4 82.1 80.1 73.9
C~3) 43.9 46.4 43.8 48.0 60.8 63.2
(1) - Composition of Example 2
~2) - Composition of Example 2 with untreated QCF in
lieu of "Water-Soluble" QCF (Fraction #3, Example 1)
(3) - Composition of Example 2 with no soil release
promoting polymer of fraction thereof.
Thus, besides exhibiting excellent physical stability
the "water-soluble" fraction compositions exhibited excellent
chemical stability.
~ 43
