Note: Descriptions are shown in the official language in which they were submitted.
This invention relates to detergent compositions which
are useful for washing synthetic organic polymeric fibrous materials,
such as polyesters, and which impart soil releasing properties to such
washed materials. More particularly, the invention relates to such
compositions which contain a particular type of polymer of polyethylene
I 2301-1226
terephthalate and polyoxyethylene te.ephthalate which not only
imparts soil release characteristics to the washed material but
also, unlike some other soil release agents, does not so change
the characteristics of the washed material as to make it
appreciably less comfortable by preventing or objectionably
diminishing vapor transmission through it. The invented compost
lotions also have been found to inhibit redeposition ox soil onto
the washed material. The invention also relates to processes for
rnakiny and using the described compositions.
The technical literature includes disclosures of
polymeric materials having both hydrophilic and lipophilic prop-
reties which can be applied to fibrous substrates to promote
soil release therefrom. Such materials are believed to form a
coating on the fibers, to which coating the soiling material,
such as an oily or greasy substance does not adhere as strongly
as it would to the substrate fibers. Thus, during washing of
laundry any soil is more readily removed from materials that
have previously been treated with a soil release promoting
polymer. Although such a polymer may be applied to a textile
material or clothing article when it is being manufactured such
an application may be insufficient to keep the item soil release
in during all of its intended life. Also, if a heavy applique-
tion of the polymer is applied at the time of manufacture it may adversely affect the properties of the fabric, as by making it
less capable of moisture transmission and -thereby making it less
comfortable to a wearer of a clothing item made from such treated
material. Additionally, comparatively heavy applications of the
polymer can adversely affect the feel of the fabric.
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2301-1226
The problems mentioned above can be avoided by apply-
in smaller proportions of a soil release promoting polymer
periodically during the life of a garment or other textile pro-
duct. One way of accomplishing this is by incorporating such
material in a detergent composition with which the item will be
periodically washed. Thus, theoretically at least, during
washing the polymer will be deposited on the fibrous substrate,
where it will remain during rinsing and drying, so that any
soiling material that is subsequently deposited on the washed
I article will be more readily released during the next washing.
Although the concept is relatively simple theoretically, as a
practical matter it may be very difficult to formulate a deter-
gent composition including a soil release promoting polymer so
that the composition will produce the desired effects. Thus, the
composition should be compatible with the detergent and builder
(and an adjutants present), should be sufficiently substantive
to the textile material so as to be deposit able thereon from
the dilute washing solution, should not adversely affect the
vapor transmission or feel of the textile, should not give the
textile an objectionable appearance and should not build up
objectionable concentrations on the -textile despite repeated
washes. A suitable polymer will possess a special balance of
properties and so will the detergent composition incorporating
it, to make them commercially acceptable. Also, the soil release
promoting detergent composition will be of such characteristics
that when it is added to the wash water objectionable reactions
with the wash water ions and/or with solubilized components of
-- 3 --
Fed 2301-1226
the composition, which could inactivate the polymer, do not
occur.
One way of stabilizing the soil release promoting
agent so that it does not lose an excessive proportion of its
release promoting characteristic on storage is to "insulate" it
from materials that tend to react with it. It has been noted
that various water soluble salts and builders which are useful
in detergent compositions may adversely affect the stabilities
in wash water of soil release promoting copolymers of polyethyl-
one terephthalate and polyoxyethylene terephthalate. Such destabilization is of greatest concern when the builder salts
or other components of the detergent composition are water
soluble and are alkaline in aqueous media. Detrimental hydra-
louses or other adverse reactions with the soil release polymer
have been noted at oh's of or more, ego, 9-11, and such
degradation or alteration of the polymer so that it loses its
desirable soil release promoting characteristics becomes more
severe as the pi is increased. In addition, it has been found
that the presence of anionic detergent(s) can promote such
destabilization. Apparently, any adverse reaction in the wash
water between builder salts and the release polymer, when the
builder and polymer are in a non ionic detergent composition or
are used with such a detergent, either does not occur or does
not prevent the polymer from being effective to promote soil
release from washed laundry. However, the presence of anionic
detergent and/or alkaline builder with the soil release polymer
in a liquid product or particulate product containing sufficient
moisture to facilitate hydrolysis of the polymer can cause
losses yin soil release properties during storage, especially if
-- 4
I
2301-1226
that Syria is under high temperature, high humidity conditions.
Therefore, it is desirable for detergent compositions containing
soil release promoting polyesters, such as those mentioned
herein, to be non-alkaline, an hydrous (or nearly so) and non-
anionic. However, as a practical matter some moisture will
normally be present in the detergent compositions and many
effective builders for such compositions are alkaline. Thus,
for detergent compositions in which alkaline builders are to be
employed and which may contain moisture, either initially, or
absorbed during storage, it is important to prevent or suffice-
entry limit any adverse reaction of sail release promoting polyp
men with alkaline material.
It has been found that by a method described herein
the soil release promoting copolymer may be uniformly duster-
butted throughout the particulate detergent product and such
product will be satisfactorily free flowing and uniform in
appearance. Also, upon addition of the detergent composition
to the wash water it will dissolve readily and the polymer will
be quickly and uniformly distributed throughout the wash water.
such method requires little extra equipment, and additional pro-
cussing time needed is minimal. Also, although the copolymer
is homogeneously distributed throughout the detergent composition
it is largely insulated from adverse reaction with any alkaline
material, especially when moisture contents of the polymer and
base beads are lower, and therefore is less subject to hydrolysis
or other detrimental reaction which could reduce its soil release
promoting activity.
In accordance with the present invention a paretic-
slate built non ionic synthetic organic detergent composition for
washing synthetic organic polymeric fibrous materials comprises
from 5 to 30~ of synoptic organic non ionic detergent, 30 to 80%
of builder(s) for such detergent, 1 to 20% of water, and a per-
cent age, within the range of 0.5 to 20%, sufficient to impart
soil release properties to synthetic organic polymeric fibrous
materials washed with the detergent composition while maintaining
them comfortable to a wearer and not preventing vapor transmission
through them, of a polymer of polyethylene terephthalate and
polyoxyethylene terephthalate ova molecular weight in the range
of about 8,000 to 60,000, preferably 15,0Q0 to 50,000, wherein
the polyoxyethylene of the polyoxyethylene terephthalate is of a
molecular weight in the range of about 1,000 to 10,000, and the
molar ratio of ethylene terephthalate to polyoxyethylene turf-
thalate units is within the range of 2:1 to 6:1. Preferably,
the detergent composition is of a bulk density in the range of
I or 0.5 to 0.9 gag but it can be decreased to as low as
0.2 CJ. /CC., the non ionic detergent is a condensation product of
a higher fatty alcohol of 12 to 16 carbon atoms with 3 to 20 mows
of ethylene oxide, the builder is selected from the group con-
sitting owe water softening zealots, sodium carbonate, sodium
bicarbonate sodium tripolyphosphate, sodium pyrophosphate,
sodium nitrilotri.acetate and sodium silicate, and mixtures there-
of, the polymer is of a molecular weight in the range of about
19,000 to 25,000, the polyoxyethylene of
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I 8 2301-1226
the polyoxyethylene terephthalate is of a molecular weight
in the range of 3,000 to ~,000, the molar ratio of ethylene
terephthalate to polyoxyethylene terephthalate units in the
polymer is within the range of 3:1 to 4:1, the molar ratio ox
ethylene oxide to phthalic moiety therein is from 20:1 to 30:1,
and the percentage of polymer present is in the range of 1 to
106, more preferably 2 to 5%.
The invented compositions are preferably employed in
a washing method of the invention which comprises washing
synthetic organic polymeric fibrous materials in an aqueous
medium in a washing machine tub, which medium contains from
0.005 to 0.15% of synthetic organic non ionic detergent OWE
to 0.~0% of builder for such detergent, and a percentage,
within the range of 0.0005 to 0.10%, sufficient to impart soil
release properties to the fibrous materials being washed, of a
polymer of polyethylene terephthalate and polyoxyethylene
terephthalate of a molecular weight in the range of about
15,000 to 50,000, wherein the polyoxyethylene of the polyoxy-
ethylene terephthalate is ox a molecular weight in the range
of about 1,000 to 10,000, and the molar ratio of polyethylene
terephthalate to polyoxyethylene terephthalate units is within
the range of 2:1 to 6:1. Preferably such method is carried
out by adding a soil release promoting detergent composition of
the type hereinabove described to the wash water in a suitable
washing machine tub. Also within the invention is a particulate
built non ionic synthetic organic detergent composition or
washing synthetic organic polymeric fibrous materials and
2301-1226
imparting soil release properties to them which comprises from
5 to 30% of synthetic organic non ionic detergent, 30 to 80%
of builder for such detergent, 1 to 20% of waxer, and a
percentage, within the range of 0.5 to 20%, sufficient to
impart soil release properties to synthetic organic polymeric
fibrous materials washed with the detergent composition, of
a soil release promoting polymer of polyethylene terephthalate
and polyoxyethylene terephthalate, in which detergent compost
it ion the non ionic detergent is absorbed into absorbent part-
ales of the builder and the soil release polymer is also post-
applied to said particles.
The described detergent compositions are preferably
made 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
an hydrous soil release promoting polymer of polyethylene
terephthalate and polyoxyethylene -terephthalate and spraying
such liquid non ionic detergent - polymer mixture onto moving
surfaces of the builder particles to distribute such non ionic
detergent and polymer over such particles. Such polymer-
non ionic detergent composition is also considered -to be a part
of the present invention.
Although various non ionic detergents of satisfactory
physical characteristics may be utilized, including ~ondensa-
lion products of ethylene oxide and propylene oxide with eachothex and with hydroxyl-containing bases, such as nonyl phenol
and Oxo-type alcohols, for best results it is highly preferred
that the non ionic detergent be a condensation product of ethyl-
one oxide and higher fatty alcohol. In such products the
higher fatty alcohol is of 10 -to 20 carbon atoms, preferably
12 to 15 or 16 carbon atoms, and the non ionic detergent contains
by
2301-1226
from about 3 to 20 or 30 ethylene oxide groups per molt
preferably prom 6 to 11 or 12. Most preferably, the non ionic
detergent will be one in which the higher fatty alcohol is of
about 12 to 15 or 12 to 14 carbon atoms and which contains
from 6 or 7 to 11 mows of ethylene oxide. Among such detergents
is Alfonic 1214-60C, sold by the Kink division of
ELI. Dupont de Numerous, Inc., and Noodles 23-6.5 and 25-7,
available from Shell Chemical Company. Among their especially
attractive properties, in addition to good detergency with
respect to oily and greasy soil deposits on goods to be washed,
and excellent compatibility with the present polymeric release
agents, is a comparatively low melting point, often in the
range of about 40 or 45 to 65C., e.g., 45 to 50C., which
is still appreciably above room temperature, so that they
may be sprayed onto base beads as a liquid which solidifies
quickly after it has penetrated into the beads. Sometimes
non ionic detergents of melting points as low as 30C. or 35C.
may be used but because such could liquefy when the product is
used (and stored) in hot climates such detergents may often
be avoided.
Various builders and combinations thereof which
are effective to complement the washing action of the non ionic
synthetic organic detergent(s) and to improve such action
include both water soluble and water insoluble builders. Of
..~
2301-1226
the water soluble builders, which preferably are employed in
mixture, both inorganic and organic builders may be useful.
Among the inorganic builders those of preference include :
various phosphates, preferably polyphosphates, such as the
tripolyphosphates and pyrophosphates, more specifically the
sodium tripolyphosphates and sodium pyrophosphates, e.g.,
pentasodium -tripolyphosphate, tetrasodium pyrophosphate;
sodium carbonate; sodium bicarbonate; and sodium silicate;
and mixtures thereof. Instead of a mixture of sodium carbonate
and sodium bicarbonate, sodium sesquicarbonate may often be
substituted. Roy sodium silicate is normally of Nash
ratio within the range of 1:1.6 to 1:3, preferably 1:2.0 to
1:2.4 or 1:2.8, e.g., 1:2.4. Of the water soluble inorganic
builder salts the phosphates will usually be employed with a
lesser proportion of sodium silicate, the carbonate will be
employed with bicarbonate and often with a lesser proportion
of sodium silicate, and the silicate will rarely be used alone.
Instead of individual polyphosphates being utilized it will
sometimes be preferred to employ mixtures of sodium purifies-
plate and sodium tripolyphosphate in proportions within the range of 1:10 to 10:1, preferably 1:5 to 5:1. Of course, it
is recognized that changes in phosphate chemical structure
may occur during crutching and spray drying, so that the
final product may differ somewhat prom the components charged
to the crutches.
10 --
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2301-1226
Of the water soluble organic builders nitrilotriacetic
acid salts, e.g., trisodium nitrilotriacetate NUT preferably
employed as the MindWrite, are preferred. Other neutral
triacetates, such as disodium nitrilotriacetate, are also useful.
The various water soluble builder salts may be utilized in
hydrated forms, which are often preferred. Other water soluble
builders that are considered to be effective include the
inorganic and organic phosphates, borate, e.g., borax, citrates,
yluconates, ethylene Damon tetraacetates and iminodiacetates.
Preferably the various builders will be in the forms of their
alkali metal salts, either the sodium or potassium salts,
or mixtures thereof, but sodium salts are normally more
preferred. In some instances, as when neutral or slightly
acidic detergent compositions are being produced, acid forms
of the builders, especially of the organic builders, may be
preferable but normally the salts will either be neutral or
basic in nature, and usually a I aqueous solution of the deter-
gent composition will be of a pi in the range of 9 to 11.5,
e.g., 9 to 10.5.
Although insoluble builders generally of the
zealot type, may be used advantageously in the compositions
of the present invention, hydrated Zealot A will be employed
most frequently. Nevertheless, Zealots X and Y may be
useful too, as may be naturally occurring zealots and
zeolite-like materials and other ion-exchanging insoluble
2301-12~6
compounds that can act as detergent builders. Of the various
Zealot A products, Zealot I has been found to be preferred.
Such materials are well known in the art and methods for
their manufacture need not be described here. Usually such
compounds will be of the formula
( 2 )X-(Al2O3)y-(sio2~z-w HO
wherein x is 1, y is from 0.8 to 1~2, preferably about 1, z
is from 1.5 to 3.5, preferably 2 to 3 or about 2, and w is
from 0 to 9, preferably 2.5 to 6.
The zealot builder should be a univalent cation-
exchanging zealot, i.e., it should be an aluminosilicate of
a univalent cation such as sodium, potassium, lithium (when
practicable) or other alkali metal or ammonium. Preferably
the univalent cation of the zealot molecular sieve is an
alkali metal cation, especially sodium or potassium, and
most preferably it is sodium. The zealots, whether crystalline
or amorphous, are capable of reacting sufficiently rapidly with
calcium ions in hard water so that, alone or in conjunction
with other water softening compounds in the detergent
composition, they soften the wash water before adverse reactions
of such ions with other components of the synthetic organic
detergent composition occur. The zealots employed may be
characterized as having a high exchange capacity for calcium
- 12 -
I 2301-1226
ion, which is normally from about 200 to 400 or more milligram
equivalents of calcium carbonate hardness per gram of the
aluminosilicate, preferably 250 to 350 my. erg on an
an hydrous zealot basis. Also they preferably reduce the
hardness quickly in wash water, usually within the first 30
seconds to five minutes after being added to the wash water,
and lower the hardness to less than a milligram of Cook per
liter within such time. The hydrated zealots will normally
be of a moisture content in the range of 5 to 30~, preferably
about 15 to 25% and more preferably 17 -to 22~, e.g., 20%.
The zealots, as charged to a crutches mix from which base
beads may be made, should be in finely divided state, with
the ultimate particle diameters being up to 20 microns, e.g.,
0.005 to 20 microns, preferably 0.01 to 8 microns mean
particle size, e.g., 3 to 7 microns, if crystalline, and 0.01
to 0.1 micron, e.g., 0.01 to OWE micron, if amorphous.
Although the ultimate particle sizes are much lower, usually
the zealot particles will be of sizes within the range of
No. 100 to 400 sieve, preferably No. 140 to 325 sieve, as
charged to the crutches for the manufacture of the base beads.
In the base beads the zealot will often desirably be
accompanied by a suitable builder salt or salts, e.g., sodium
carbonate, sodium bicarbonate. Sodium silicate may tend to
agglomerate with zealots so the proportion thereof present in
zeolite-built base beads may be limited, as to 2 or 3%, or it
may be omitted, especially for carbonate-containing formulations,
but sometimes as much as 5 to 10% may present, as in NTA-built
products.
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2301-1226
Although water soluble builders are useful with the
soil release promoting polymers in the present detergent
compositions adverse interactions between the polymer and
water soluble salts in the presence of moisture are possible
especially when the composition is basic in nature, e.g., with
a pi above 8. Since moisture is a component of the present
detergent composition particles, and its presence does help such
particles to be held together better and be less friable, it
may often be preferable to utilize insoluble builders, like the
ion exchanging zealots, which may be less reactive with the
polymer and thereby may provide compositions with better soil
release promoting powers despite lengthy storage in humid
atmospheres. The hydrated zealots of less than full hydrating
capacity may be useful in this respect because they tend to
absorb excess moisture, which can inhibit adverse reactions of
any soluble alkaline salts with the polymer in -the presence of
such moisture.
The soil release promoting polymer which is an
important component of the compositions of this invention is
a polymer of polyethylene terephthalate and polyoxyethylene
terephthalate which is dispersible in water and is deposit able
From wash water containing non ionic detergent and builder for
the non ionic 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 polyesters
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
- 14 -
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2301-1226
redeposited on the laundry. Useful such products are copolymers
of ethylene glycol or other suitable source of ethylene oxide
moiety, polyoxyethylene glycol and terephthalic acid or suitable
source of the terephthalic moiety. The copolymers may also be
considered to be condensation products of polyethylene turf-
thalate, which may sometimes be referred to as an ethylene
terephthalate polymer, and polyoxyethylene terephthalate. While
-the terephthalic moiety is preferred as the sole dibasic acid
moiety in the polymer it is within the invention to utilize
relatively small proportions of isophthalic acid and/or
orthophthalic acid Rand sometimes other dibasic acids, too)
to modify the properties of the polymer. However, the proper-
lions of such acids or sources of such moieties charged to any
reaction mix and the corresponding proportions in the final
polymer will normally be less than 10% each of the total phthalic
moieties present and preferably will be less than I thereof.
For best characteristics the molecular weight of the
polymer will be in the range of about 15,000 to 50,000, prefer-
ably being about 19,000 to 43,000, more preferably being about
19,000 or 20,000 to 25,000, e.g., about 22,000, but sometimes
may be as low as 8,000 or as high as 60,000. Such molecular
weights are weight average molecular weights, as distinguished
from number average molecular weights which, in the case of
the present polymers, are often lower. In the polymers
utilized the polyoxyethylene will be of a molecular weight in
the range of about 500 or 1,000 to 10,000, preferably about
2,500 to 5,000, more preferably 3,000 to 4,000, erg., about
3,400, In such polymers the molar ratio of polyethylene
terephthalate to polyoxyethylene terephthalate units (consider-
in ,, A n n A ,.
OCH2CH2O-C- I and ~(OCH2CH2)n-O-C- I
I
2301-1226
as such units) will be within the range of 2:1 to 6:1, highly
preferably 5:2 to 5:1, even more preferably 3:1 to 4:1, e.g.,
about 3:1. The proportion of ethylene oxide to phthalic moiety
in the polymer will be at least 10:1 and often will be 20:1 or
more, preferably being within the range of 20:1 to 30:1 and
more preferably being about 22:1. Thus, it is seen that the
polymer may be considered as being essentially a modified
ethylene oxide polymer, with the phthalic moiety being only a
minor component thereof, whether calculated on a molar or weight
basis. It is considered surprising that with such a small
proportion of ethylene terephthalate or polyethylene turf-
thalate in the polymer the polymer is sufficiently similar to
the polymer of the polyester fiber substrate (or other polymers
to which it is adherent, such as polyamides as to be retained
thereon during the washing, rinsing and drying operations. Yet,
as shown by comparative experiments and various washing tests
in which soil release is measured, the described polymer, in
the present detergent compositions, is effective to deposit on
washed synthetics, especially polyesters, and to make them better
able to be washed free of oily soil by a built non ionic detergent
composition. It is considered that its increased hydrophilicity,
attributable to the large proportion of hydrophilic ethylene
oxide moieties therein, may be responsible for the excellent soil
release properties which it imparts to the material upon which
it is deposited, and such may also help it to cocci with the
built non ionic detergent.
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2301-1226
Although suitable methods for making the instant
polymers are described in the literature it is considered that
none of them discloses the particular described polymers and
none discloses the present detergent compositions. Such
polymers may be considered as having been randomly constructed
from polyethylene terephthalate and polyoxyethylene terephthal-
Tao 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 methyl ester) precursors thereof. Yet,
it is also within the invention to utilize more ordered
copolymers, such as those made by reacting components of prey
determined or known chain lengths or molecular weights, so as
to produce what might be referred to as block copolymers
or non-random copolymers~ Graft polymers may also be practice
able. Also, the described processes of making useful soil
release promoting detergent compositions are also practicable
with other polyethylene terephthalate - polyoxyethylene
terephthalate copolymers, and the non ionic detergent - polymer
solutions or dispersions can be made from such other polymers.
The described materials are available from various
sources the products of one of which will be described in more
detail here. Useful copolymers for the manufacture of the
2301-1226
detergent compositions of this invention are marketed by
Alk~ril Chemicals, Inc., and commercial products of such
company that have been successfully employed to produce sails-
factory soil release promoting detergent compositions are those
sold by them under the trademarks Alkaril QCJ and Alkaril QCF,
formerly Quaker QCJ and Quaker QCF. Products available from
them in limited quantities, designated by them as 2056-3~B
and 2056-41, have also been found -to be acceptable. The QCJ
product, normally supplied as an aqueous dispersion, is also
available as an essentially dry solid. When it it an hydrous
or low in moisture content (preferably less than 2% moisture),
it looks like a light brown wax in which the molar ratio of
ethylene oxide to phthalic moiety is about 22-1. In a 16%
dispersion the viscosity at 100F., is about 96 centistokes.
The 2056-~1 polymer is like a hard, light brown wax and in it
the hydrophile:hydrophobe ratio is about 16 to 1, with the
viscosity being about 265 centistokes. The 2056-3~ polymer
appears to be a hard brown wax, with a hydrophile:hydrophobe
ratio of about 10.9.1 and its viscosity, under the same con-
dictions as previously mentioned, is about 255. Thus, Thor the molecular weight of the polymer the lower the
hydrophile:hydrophobe molar ratio may be therein and still no-
suit in satisfactory soil release promotion by the invented
detergent compositions. The QCJ and QCF polymers have melting
points (by differential thermal analysis) of about 50 to 60C.,
a carboxyl analysis of 5 to 30 equivalents grams and a pal
of 6 to 8 in distilled water at 5% concentration. The molecular
weights (weight average) are in the range of 20,000 to 25,000
-- 18
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2301-1226
and -the ethylene terephthalate:polyoxyethylene terephthalate
units molar ratio is about 74:26. ~11 three of the mentioned
trademarked products are water soluble in warm or hot water
(at 40 to 70~C.) or at least are readily dispersible, and may
be characterized as of high molecular weight, over 15,000,
generally in the range of 19,000 to 43,000, often preferably
20,000 to 25,000, e.g., about 22,000. Normally, for "solution"
application to materials or for solution addition to a deter-
gent composition in wash water, the copolymers of this invention
may be employed in aqueous dispersion. In such dispersions a
surface active agent may be present to assist in maintaining
the dispersion uniform. Only small proportions of such surface
active agent will be employed, if any, and among -those -that
have been found to be useful are the qua ternary ammonium
halides and other suitable cat ionic surface active agents.
Normally, the concentration of the polymer in the aqueous
medium will be about 5 to 25%, on a composition basis, prefer-
ably 10 to 20%, e.g., 15%, and such is the concentration at
which the mentioned commercial products are normally supplied
when a liquid form is desired. Generally, the proportion of
cat ionic surface active agent present, if any at all, will be
from 0.5 to 5%, preferably 1 to 3%, e.g., 2%, in the liquid
preparation, or 3 to 30%, preferably 5 to 20%, e.g., 13% with
the solid polymer. While liquid dispersions or solvent soul-
- 19 -
2301-1226
lions of the polymer may be employed for direct additions of
the polymer to the medium in which the fabrics are to be treated,
when the polymer is to be incorporated in a particulate deter-
gent composition it will be preferable for it to be in solid
form, preferably as a particulate solid of a particle size like
that of the other detergent composition components. Alterna-
lively, it may be finely divided and powdered onto spray dried
beads of the other components. In more preferred methods of
incorporation in a detergent composition the polymer may be
dissolved in non ionic detergent, preferably essentially an hydrous,
and sprayed onto base beads/ but it may also be pilled with
carriers and mixed with the base beads. It has been found that
the polymer should not be added to an aqueous crutches mix
containing anionic detergent and/or builder salt and it should
not be brought into contact with water soluble builder salt in
the presence of moisture, especially at an elevated temperature.
Accordingly, to make free flowing particulate product, normally
the polymer will be essentially dry or very low in moisture
content. The use of such a product also allows for the
manufacture of base beads at normal moisture content without
the moisture content thereof being increased objectionably by
- 20 -
2301-1226
post-spraying of an aqueous dispersion of the polymer onto the
beads.
Various suitable adjutants may be present in the
invented detergent compositions, such as bentonite, which
contributes softening properties to the product and helps
cause the product to disperse rapidly in wash water; polyp
acrylate which desirable promotes dispersion of the product
and provides bead strength and bulk density and porosity control
(and also, like the bentonite, helps to promote spray drying
and improve drying efficiency); enzyme powder which helps
to decompose stains and other soils so as to promote their
removal, thereby coating with the soil release promoting
polymer; perfumes; fluorescent brighteners; bleaches, e.g.,
sodium perorate; colorants (dyes and water dispersible pigments,
such as ultramarine blue); bactericide; fungicides; and flow
promoting agents; some of which materials may be added in
the crutches so that they are parts of the base beads, and
some of which may be post-added. Inorganic fillers, such as
sodium sulfate and sodium chloride, may be utilized but
preferably the proportions thereof will be limited because it
has been found that sodium sulfate tends to react adversely
with the present polymers. Of the enzymes, both proteolytic
and amylolytic enzymes may be employed, such as those sold
under the trademarks Alkalis, manufactured by Nova Industry,
A/S, and Maxazyme, both of which are alkaline pro teases
(subtilisin).
- 21 -
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2301-1226
In the invented detergent compositions the proper-
lion of synthetic organic non ionic detergent will be from 5 to
30%, preferably 10 to 25% and more preferably 18 to 22%, e.g.,
about 20%. The proportion of builder w-11 be from 30 to 80%,
preferably from 40 to 80%, more preferably 50 to 75%. The
proportion of soil release promoting polymer will be from 0.5
to 20~, preferably 1 to 10%, more preferably 1 to 5% and
most preferably 2 to 5%, e.g., 3%. The moisture content of
-the product will be from 1 to 20%, preferably 2 to 15% and
more preferably 2 to 10 or 12%. The moisture content may be
higher with compositions in which the builder is a partially
hydrated zealot and which do not contain sodium sulfate.
Individual adjutants are preferably no more than 10% of the
composition, more preferably being limited to 5% and often
to 2 or 3%, with the total of adjutants desirably not exceeding
25%, preferably being limited to 15% and more preferably being
held to 5 or 10~ of the composition (except when bentonite) is
one of such adjutants, in which case the proportion thereof may
be increased by up to 5 or 10%.
When bentonite is present it will preferably be a
swelling bentonite of the Wyoming type, such as that which has
been sold under the trademark THIXO-JEL No. 1 (now Mineral
Killed 101), normally with a swelling capacity in water in
the range of 3 to 15 mug preferably 7 to 15 mug and
with a viscosity in water in the range of 3 to 30 centipoises,
preferably 8 to 30 centipoises at a I concentration. The
- 22 -
;''''`'''
I 2301-1226
proportion of bentonite, when it is present in the detergent
composition, will usually be in the range of 2 to 10%,
preferably 4 to 10%. Sodium polyacrylate or other suitable
water soluble polyacrylate, when present, will normally be at
a concentration within the range of Cot to 1%, preferably 0.1
to 0.5%. Enzyme powder, when present, will usually be at a
concentration in the range of 0.5 to 3%, preferably 1 to 2%.
Such enzyme powder is commercially available as a mixture of
active enzyme and carrier material, e.g., Maxazyme 375.
For those detergent compositions wherein zealot is
present with sodium carbonate and sodium bicarbonate, the
percentages thereof will usually be within the range of 20 to 35-~,
5 to 15% and 15 to 30%, respectively preferably 25 to 30%, 9
to 14% and 20 to 25%. In such compositions silicate will
preferably be avoided or limited to about 2 or 3% of the product,
and the moisture content will usually be in the range of 4 to
12%, preferably 6 to 10%. Enzyme, bentonite and sodium posy
acrylate will preferably also be present in such products and
sometimes more silicate can also be tolerated, as in NTA-built
products. For compositions built with carbonate, bicarbonate
and sodium silicate, the proportions will usually be 15 to 35%,
20 to 40% and 3 to 15%, respectively, preferably 20 to 30%,
30 to 35% and to 13%, respectively. Enzyme powder will
normally also be present and the moisture content will normally
I
2301-1226
be in the range of 2 to 10%, such as 2 to 6%. Other preferred
compositions based on combinations of zealot, NAT, sodium
silicate and sodium carbonate will include 20 to 35%, 15 to
40%, 2 to 10%, and 1 to 10% of such materials, respectively,
preferably 20 to 30%, 25 to 35%, 3 to I% and 2 to I respect
lively. Such products will also desirably contain enzyme, and
their moisture contents will usually be in the range of to 12%,
preferably 3 to 8%. For phosphate formulas, those wherein the
builder is sodium polyphospha-te, such as sodium tripolyphosphate,
with silicate, the proportions of such materials will normally be
in the ranges of 40 to 75% and 5 to 15%, respectively,
preferably 50 to 70% and 6 to 12%, with the moisture content
thereof being from 4 to 12%, preferably from 6 to 10%. Such
compositions will also preferably contain an enzyme powder.
The compositions described will usually also contain a
fluorescent brightener, such as that sold under the trademark
Tin opal IBM, a perfume, and optionally, a coloring agent, such
as ultramarine blue, Polar Brilliant Blue or Blue Dye No. 5.
When setting in the crutches is a possibility, due to the nature
of the crutches mix, such as one containing carbonate, bicarbon-
ate and silicate-built base beads, anti-gelling or anti-setting
agents, such as mixtures of magnesium sulfate and sodium citrate,
may be employed and such will then be present in the end product.
- 24 -
230~-1226
The detergent compositions, whether previously
manufactured and stored before use, or made immediately prior
to use, may be employed in dilute aqueous solution (or dispel-
soon) in wash water to wash all-synthetic materials, including
polyester; cotton-synthetic blends, including cotton-polyester
blends; cottons; nylons; and mixtures of such materials.
normally the weight ratio ox the dry weight of materials being
washed to aqueous washing medium will be in the range ox 1:20
to 1:5, preferably 1:20 to 1:9, the wash will be conducted with
agitation over a period from 5 minutes to 1/2 hour or one hour,
often from 10 to 20 minutes, and after washing the materials
will be rinsed, usually with several rinses, and will be dried,
as in an automatic laundry dryer. The wash water will usually
be at a temperature of 10 to 60C., preferably 20 to 50C. and
more preferably 40 to 50C., and the concentration of the deter-
gent composition or the equivalent components (if
separately added to the wash water) will be from 0.05 to 1%,
preferably from 0.05 to 0.15%, e.g., 0.06% or 0.13%~ More
preferred detergent compositions have a bulk density in the range
ox 0.6 to 0.9 gag and such detergents are normally employed
at a concentration of about 1/4 cup (or about 40 grams) per
wash, with the wash tub usually containing about 17 gallons
(US.) ox water for top loading machines and about 7 to 8 gallons
or front loaders. When a "European" type of washing machine
is employed wherein higher concentrations of detergent compost
it ion are utilized with lesser amounts of water, and
25 -
2301-12~6
normally higher washing temperatures are used, it may be
preferable to lower the washing temperatures for best depositing
of the polymer on the washed materials. The upper parts of the
ranges of detergent composition concentrations previously given
may be considered as appropriate for European washing conditions
whereas the corresponding lower parts of such ranges are for
"American" type top loading washer apparatuses ail conditions,
with the American front loader concentrations being somewhat
intermediate.
The proportions of the individual active components
of the present compositions in the wash water will normally
be from 0.005 to 0.15% of synthetic organic non ionic detergent,
0.03 to 0.4% of builder for such detergent and 0.0005 to
0.10% of polyethylene terephthalate - polyoxyethylene terephthal-
ate copolymer. Preferably such proportions will be 0.005 to
0.06%, 0.03 to 0.16% and 0.0005 to 0.04~, respectively, and
more preferably 0.01 to 0.05%, 0.03 to 0.14~ and 0.0005 to
0.02%, respectively. Most preferably the percentage of the
polymer present will be in the range of 0.001% to 0.01%, e.g.,
0.002~. While such ranges apply to both horizontal and vertical
tub machines the horizontal tub sometimes requires lessor
proportions of -the composition per unit weight of laundry for
equal cleaning power. For soil release however, it is advisable
to employ concentrations within the ranges given, and to use
the amounts of polymer mentioned, although when extra polymer
is present less detergent composition may be used
26 -
!
Al 2301-1226
The base beads which may be employed in making the
compositions of the invention are preferably spray dried from
an aqueous crutches mix which normally will contain from about
40 to about 70 or 75% of solids, preferably 50 to 65~ thereof,
with the balance being water, preferably deionized water, as
previously described (but city water may also be employed).
the crutches mix is preferably made by sequentially adding
various components thereof in a manner which will result in the
most miscible, readily pump able and non-setting slurry for
spray drying. The order of addition of the materials may be
varied, depending on the circumstances, but it is highly
desirable when "wettable" crutches mixes are employed to add
the silicate solution (if any) last, and if not last, at least
after the addition of any gel- or freeze preventing combination
of materials or processing aids/ such as citric acid and mug-
noisome sulfate. Normally it is preferable for all or almost
all of the water to be added to the crutches first, preferably
at about the processing temperature, after which the processing
aids (if present) and other minor components, including pigment,
fluorescent brightener and polyacrylate, if present, are
added, followed by most of the builder(s), bentonite and sift-
gate builder (if present). Usually during such additions each
component will be mixed in thoroughly before addition of the
next component but methods of addition may be varied, depending
- 27 -
2301-1226
on the circumstances, so as to allow co-additions when such
are feasible. Sometimes component additions ma be in two
or more parts and sometimes different components may be
premixed before addition to speed the mixing process.
Normally, mixing speed and power will be increased as the
materials are added. For example, low speed may be used until
after admixing in of the last of the zealot or soluble builder,
after which the speed may be increased to medium and then to
high, at which it will preferably be before, during and after
addition of any silicate solution.
The temperature of the aqueous medium in the crutches
will usually be about room temperature or elevated, normally
being in the 20 to 80C~ range, preferably from 30 to 75 or
80C., and more preferably 40 to 70 or 80C. Heating the
crutches medium may promote solution of the water soluble salts
of the mix and thereby increase miscibility but -the heating
operation, when effected in the crutches, can slow production
rates. Therefore, an advantage of having processing aiding
materials present in the mix (especially if any soluble silicate
is present, is that they ensure that at lower temperatures non-
golfing slurries will result. Temperatures higher than 80~C.
(and sometimes those higher than 70C.) will usually be avoided
because of the possibility of decomposition of one or more of the
- 28 -
Lo I
2301-1226
crutches mix components, e.g., sodium bicarbonate, Also, in
some cases lower crutches temperatures increase the upper
limits of eruteher solids contents, probably due to insolubi-
living of normally golfing or setting components.
Crutches mixing times to obtain good slurries can
Mary widely, from as little as five minutes in small crutches
and for slurries of higher moisture contents, to as much as
four hours, in some eases. The mixing times needed to bring
all the eruteher mix components substantially homogeneously
together in one medium may be as little as ten minutes but in
some cases can take up to an hour, although 30 minutes is
a preferable upper limited. Counting any such initial admixing
times, normally crutching periods will be from 15 minutes to
two hours, e.g., 20 minutes to one hour, but the crutches mix
should be such as to be mobile, not golfed or set, for at
least one hour, preferably for two hours, and more preferably
for four hours or longer after completion of the making of
the mix, and preferably will be mobile for as long as 10 to
30 hours to allow for situations wherein other manufacturing
problems may be encountered, causing processing delays.
The crutched slurry, with the various salts and
other components thereof dissolved or in particulate form and
uniformly distributed therein, is transferred in usual manner
to a spray drying tower, which is normally located near the
eruteher. The slurry is dropped from the bottom of the eruteher
- 29 -
, .
`!
2301~1~26
to a positive displacement pump, which forces it at high
pressure through spray nozzles at the top of a conventional
spray tower (countercurrent or concurrent) wherein the droplets
of the slurry fall through a hot drying gas, usually the
combustion products of fuel oil or natural gas, in which the
droplets are dried to desired bead form. During the drying,
part of the bicarbonate (if present) may be converted to car-
borate, with the release of carbon dioxide, which, in conjunction
with the small contents of polyacrylate (if present) in the
mix being spray dried, improves the physical characteristics
of the beads made, and helps them become more absorptive of
liquids, such as liquid non ionic detergent, which may be post-
sprayed onto them subsequently. However, the zealot Kenton-
tie and polyphosphate (when present) components of the base beads
made also appear to favor absorption of liquid and the production
of a strong bead/ and the polyacrylate improves bead character-
is tics and promotes faster drying, thereby increasing tower
throughput.
After drying the product is screened to desired size,
e.g., 10 to 60 or 100, US. Sieve Series, and is ready for
application of non ionic detergent spray thereto. Although the
foregoing description is of the making of spray dried base
beads, and such are preferred for various reasons already
mentioned, such as bulk density, uniformity, flyability,
strength and sorption properties, it is within the invention to
- 30 -
I
2301-1226
employ other equivalent or nearly equivalent base beads, such
as those which are agglomerates, mixes granulates, grinds,
pills or chopped filaments. The non ionic detergent will
usually be at an elevated temperature, such as 30 to 60C~,
e.g., 50C., to assure that it will be liquid; yet, upon
cooling to room temperature it will desirably be solid, often
resembling a waxy solid. Even if at room temperature the
non ionic detergent is somewhat tacky, this characteristic
does not make the final composition poorly flowing because the
detergent penetrates to below (or within) the bead surface.
The detergent also acts to cover the builder and any other
components of the base bead and thus protects any post-applied
polyester from contact and reaction with the base bead which
might otherwise occur, especially when the builder is alkaline
and water soluble, and the composition is stored under a humid
atmosphere. Incidentally, the presence of only partially
hydrated zealot in the compositions can lower the relative
humidity in sealed containers of the detergent r thereby also
aiding in inhibiting hydrolysis of the polyester. The non ionic
detergent, applied to moving or tumbling beads as a spray or
as droplets, is preferably a condensation product of ethylene
oxide and higher fatty alcohol, such as was previously described,
but other nonionics may also be operative. The enzyme prepare
lion (herein referred to as enzyme, although it is recognized
I
2~3~
2301-1226
that it includes a carrier material, too), hydrous silicate, if
employed, soil releasing polymer, and any other powered
adjutants may be dusted onto or mixed with the builder base
particles, and perfume and any other liquids to be post-added
may be sprayed on at a suitable point before or after addition(s)
of the powder(s). When soil release promoting polymer is
applied in or with non ionic detergent it is preferred that
the base beads, as well as the polymer-detergent, be at an
elevated temperature/ e.g., 50 to 60C., so that penetration
I of the mixture into the base beads may be promoted and so that
stable free flowing products will be obtained. The non ionic
detergent, by enveloping the polymer, or at least, by diluting
it, may act to limit contact thereof with the builder salt,
thereby stabilizing the polymer and improving soil release by
it. Although bentonite may be crutched with the other coupon-
ens of the crutches mix, and such procedure is preferred,
instead (or also) it may be post-added to the base beads or to
the base beads with detergent already absorbed therein, either
as a powder or as an agglomerate, and if it is added with the
polymer it can help to limit contact of the polymer with the
builder, and can thereby help to stabilize the composition.
Similar effects can be obtained by premixing the polymer, in
powdered or other suitable form, with other chemically non-
reactive materials.
: "!
fly
2301~1226
The preferred method of applying the polymer and
non ionic detergent to base beads includes 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 anh~drous soil release promoting
polymer and spraying such liquid non ionic detergent - polymer
mixture onto moving surfaces of the builder particles to disk
tribute such non ionic detergent and polymer over such particles.
More preferably, the soil release promoting polymer is like
the preferred ones previously described, the non ionic detergent
is a condensation product of a higher fatty alcohol of 12 to
16 carbon atoms with 3 to 20 mows of ethylene oxide per mow
of higher fatty alcohol, the builder base beads onto which the
non ionic detergent - polymer solution is sprayed include from
60 to 99Q6 of builder and 1 to 20% moisture, and the final deter-
gent composition made includes from 5 to 30% of non ionic
synthetic organic detergent, 30 Jo 80% of builder or mixture
of builders in such detergent, 1 to 20% of water and 0.5 to 20%
of soil release promoting polymer.
The non ionic detergent - polymer solutions and/or
dispersions, suitable for spraying onto detergent builder
particles to produce a soil release promoting particulate built
non ionic synthetic organic detergent composition, comprise
non ionic detergent, in liquid state, having dissolved or
suspended therein a soil release promoting polymer.
I
2301-1226
Preferably, -the non ionic detergent and soil release promoting
polymer are those mentioned herein, the polymer solution
produced is of a moisture content less that 2% and the solution
it at a temperature in the range of 40 to 70C., preferably
45 or 50 to 55 or 60C., at which temperature it is desirably
sprayed onto the builder base beads to form a soil release
promoting detergent composition.
The liquid non ionic detergent - soil releasing
polymer composition, suitable for spraying onto detergent
builder base beads or other such particles to make a soil
release promoting particulate built non ionic synthetic organic
detergent composition, comprises at least a co-polymer of
polyethylene terephthalate and polyoxyethylene terephthalate
and a normally solid condensation product of higher fatty
alcohol and ethylene oxide or ethylene glycol, both of which
will be an hydrous or of very limited moisture contents, so that
the stability of the polymer will be sufficiently maintained
on reasonable storage that the detergent composition will have
acceptable soil release promoting properties. Generally -the
moisture contents of the non ionic detergent and the polymer
will be no greater than 5% each, preferably no more than 2%
each, more preferably up -to 0.5% each, most preferably up to
0.2~ each, and ideally, each will be completely an hydrous.
Correspondingly, such moisture content limits, including a
very highly preferred 0.1%, also apply to the spray composition.
Although the non ionic detergent is normally solid, some normally
liquid detergent, e.g., 5 to 10% or so, may sometimes by
incorporated with it, depending on the circumstances, including
-- 34 -
.
I
2301-1226
the flyability of the final detergent composition, and some-
-times a normally liquid detergent can be used along, although
this is not preferred.
The concentration of the polymer in the non ionic
deterrent will normally be in the range of 5 to 30~, preferably
5 to 20% and more preferably 10 to 15%, e.g., about 13%. When
other materials are also present in the non ionic detergent with
the polymer such percentages will be adjusted accordingly. The
amounts of such additional materials, such as colorants,
perfume, filler, or dispersing agent, e.g., bentonite, if
present, will be limited, with the total thereof rarely
exceeding 10~, preferably being limited to 5% and more prefer-
ably being no more than I Often any insoluble materials, such
as bentonite, will be omitted from the spray, despite some
beneficial effects thereof, because they can to some extent
inhibit penetration of the liquid material(s) into the particle
or base bead interiors, thereby sometimes causing the final
composition to be poorly flowing and somewhat tacky.
Spraying of the liquid solution or mixture at elevated
temperature onto the base beads may be effected in any of
various types of mixing apparatuses, of which tumbling drums
are often preferred. Such tumbling drums may be elongated
hollow drums, sometimes equipped with baffles or flights to
assist in forming curtains of moving base particles as the drum
rotates. Such drums may be inclined at a suitable angle,
or - 35 -
I!
2301-1226
usually from 2 to 15 from the horizontal, such as 5 to 10,
and may rotate at a syllable speed, such as from 2 to 30
revolutions per minute, usually 4 to 20 rum The tumbling
time in the drum may be from about 1 to 20 minutes, preferably
2 to 15 minutes and often around 4 to 6 minutes will be surf-
Eicient. The liquid droplets of spray may be produced using
any standard spray nozzles, and plural nozzles may also be
employed. In some cases separate nozzles may be use for
perfume and for the detergent - polymer solution. The liquid
droplets of the sprays will normally be in the 50 to 500
micron diameter range, preferably So to 250 microns, but
coarser particles may also be employed providing that absorption
is satisfactory and lumping or agglomeration is avoided.
Preferably, to avoid such lumping the liquid spray will be
directed horizontally or somewhat upwardly onto continuously
moving surfaces of the base beads being tumbled in -the inclined
drum, as they form a "curtain" of particles.
Although a tumbling drum of the type described may be
the preferred apparatus for applying the present liquid compost
it ion to base beads, it is contemplated that other such apparatuses and mixers may also be employed and although spraying of
the liquid onto a curtain of jailing (or rising) beads is
preferred, other applications of liquid to the base beads,
either as droplets, streams, films or in other forms, may also
be satisfactory in particular circumstances. While continuous
processes for applying the liquid to the base beads are pro-
furred, batch processes may also be used and often, especially
for relatively low production rates, may be more economical and
- 36 -
Lo
2301-1226
may produce more uniform products.
The following examples illustrate the invention but
do not limit it. Unless otherwise indicated, all parts are by
weight and all temperatures are in C.
- 37 -
I
O corn n Lo) N O O
O O _ No 0
I o
o o Lo o o o o
I . , . I . . , ,. . . .
o Inn o LO
to O N
O Rowley N O O O t'')
Jo . I I . N
O o
I; I OX N ~11~IJ) t Lo 3
Jo No` Ode
.0 to O OX
So
Us d.
I f-l N
Pi I 3 'I I
OH I Rowley`_ a> I) I 1 Us O I;
I Ed X o
¢ O O h Ed Ed , to,,
~"tdF~ h D I
to I r1~ Lo by in in ¢ Z to 3 O
by ~~rltD~rl O id I h id ¢ X
ED . d So ho h I' 'I
D to Do cud ~~q~tD (D En
to N ~3~rl id ho in o Jo
outed o o ted ED I to
V in O to r1 I r1 O I) ,~:
,, JO OWE 0 m Jo id to tDhD I 0 ¢
h blearily h s
- 38 -
I
o o n
I , ,
o
I , , I
o
I . . I , I
N O
I
I I l ' ' '
I
C)
Us
Pi
l Old
r-l Al
Us *
MU
TV O
r,
o
¢ do
.,~
a) 1
o
O h
I o
.9 Pi Y id t_)
Y
o
o o, o E-
- aye -
2301~1226
In each of the above compositions the base beads are
made by mixing together the indicated components in an
aqueous medium in a detergent crutches, such mix being of
all the base components at a 55% solids concentration in
deionized water at a temperature of about 60 to 70C., but
lower temperatures may be used for certain formulations.
During mixing of the various components the mixer speed is
increased to medium and ultimately to high and after addition
of all the constituents, which takes approximately fifteen
minutes, mixing is continued for about an hour (in some cases
as much as four hours of mixing may occur), during which
time some of -the water present, e.g., about 2 to 6%, may be
lost by evaporation, and may be replenished, if desired.
During the mixing time the crutches slurry is continuously
mobile and does not gel, set or cake. Because bicarbonate
partially decomposes to carbonate during spray drying, amounts
of bicarbonate and carbonate in the crusher formulations may
be varied, depending on the spray tower operating character-
is tics.
Starting about jive minutes after all the components
of the crutches mix are present, the mix is dropped from the
crutches to a pump, which pumps it at a pressure of about 21
kegs cm. into the top of a countercurrent spray tower
wherein the initial drying air temperature is about 430C. and
the final temperature is about 105C. The base beads
39 -
~L23~
2301-1226
resulting are of a bulk density of about 0.4 gag for the
first formula and about 0.7 gag for each of the other
formulas, after being screened to a particle sizes range
substantially between No. 10 and No. 60 sieve, US. Sieve
Series. Moisture contents thereof are about 9.4%, 10%, 6.9%
and 3.1~, respectively. The base beads are free flowing
(generally with about an 80~6 flow rate), non-tacky, satisfac-
gorily porous, yet firm on the surfaces -thereof and capable
of readily absorbing significant proportions of liquid non ionic
detergent without becoming objectionably tack.
Detergent products are made from the spray dried
base beads by spraying the normally waxy non ionic detergent
onto -the tumbling bead surfaces, preferably while the beads
are being mixed in a tumbling drum. Instead of Alfonic*
1214-60C, Nudely* 23-6.5, 23-7, or 25-7, and sometimes 45~11
may be substituted. The non ionic detergent employed is in
heated liquid state, at a temperature of about 45-55C. and
the quantity sprayed is such as to result in the final product
containing about 20% of non ionic detergent. In some instances,
as previously mentioned, thy soil release promoting polymer may
be dissolved in the non ionic detergent, in which case the
temperature of the non ionic detergent and the polymer will
ordinarily be in the 45 to 60C. range, preferably a-t 50-55C.
or another suitable temperature at which the polymer is soluble
TO _ 40 _
I
2301-1226
in the non ionic detergent. The proteolytic enzyme is applied in
powdered form to result in the desired concentration in the
product, and perfume is sprayed onto the product to the extent
of its desired concentration therein. The resulting detergent
compositions are of bulk densities about the same as or up to
0.1 gel higher than those of base beads, but are within
the ranges previously recited. The products are attractive
and regular in appearance, and are free flowing an non-dusting.
Similar products may be made by blending the powdered or portico--
late soil release promoting polymer of a low moisture content preferably less than 2%, with the enzyme or with some or all
of formula amounts of bentonite, and dusting the mix onto the
base beads or blending it with such beads, either before or
after application of the non ionic detergent (preferably after).
Such applications of the polymer may also be made separately
from the enzyme and/or bentonite.
The detergent composition described above are
excellent heavy duty laundry detergents and are especially use-
fur for washing household laundry in automatic washing
machines. When employed at a concentration of about 0.05 to
0.15%, e.g., 0.06% in a top loading 17 gallon capacity washer,
in the washing of normal loads of 100% polyester and 65%
polyester - 35% cotton fabrics in home laundry or commercial
washing machines, whether of the top loading or front loading
types, or at higher concentrations in European type washing
machines, the compositions perform satisfactorily, as would be
- 41 -
I
~301-1~26
expected from a knowledge of their components, with respect to
usual washing effect characteristics but additionally they
significantly promote soil release from such materials. They
are also satisfactory for washing nylons, cottons, acetates
and blends of fibrous materials and promote soil release from
such materials too, although not to the same great extent as
with the polyesters. In tests of the washing and soil release
actions of the compositions a Whirlpool Suds Saver washing
machine is used, the water temperature is about 45C. and the
water contains a total of about 200 prom harness as Cook,
of mixed calcium and magnesium ions. The washing times are
all about fifteen minutes and the laundry: water ratio is
about 1:20, by weight. Items are rinsed twice automatically
and then are dried in an automatic laundry dryer.
Soil release promotion is an important characteristic
of the invented compositions and of the disclosed washing
method because it has long been known that oily soils, such
as motor oils and greases, have an affinity for synthetic organic
polymeric fibrous materials and are often difficult to remove
from them with conventional washing preparations. Thus, the
presence of the present soil release promoting polymer signify-
gently aids in the removal of such oily soils or stains from
the laundry and improves the products' detergencies. Such
effect is more significant on repeated launderings, usually up
to five launderings of the washed materials with the present
compositions (or with equivalent wash water solutions). Yet,
despite the apparent deposition of the soil release polymer
on the substrate materials such materials do not become way
- 42 -
2301-1226
to the touch, do not change significantly in appearance or in
normal desirable characteristics and do not block or inhibit
the flow of moisture, so that evaporation of a wearer's
perspiration is not prevented. Thereby the present
compositions provide soil release without objectionable
characteristics that otherwise might attend such release and
key improve the comfort to the wearer of the washed garments.
If an hydrous or essentially an hydrous polymer is employed,
if the moisture content of the rest of the detergent compost-
lion is maintained low, not being greater than about 10% andpre~erably being held to 5% or less, if the product is not
excessively alkaline, and if storage conditions are not
excessively humid, the final compositions are of satisfactory
stability during stucco for reasonable periods, so that the
polymers do not objectionably hydrolyze or otherwise decompose
or transesterify which could adversely affect their soil release
and comfort characteristics. Even when more moisture and alkali
are present useful products are obtainable but it may be
desirable to utilize higher percentages of the soil release
promoting polymer to allow for some detrimental effects of
further decompositions on storage under adverse conditions.
In addition to users of the present products noting
the improved soil release in washing normal loads of laundry
containing articles soiled with oils or greases, comparative
tests wherein dirty motor oil is applied to
- 43 -
swatches of polyester and polyester-cotton blend materials
and such swatches are washed in either the invented compost-
-lions or control compositions, the same as those of the
invention but without the soil release promoting polymer,
also show improved soil release for the invented products
after repeated use. In such tests skilled observers note
the improvement in soil removal by the compositions of the
invention. Such results are further borne out by reflect-
meter checks of the washed materials, which also establish
that the invented compositions are of improved anti--redeposi-
lion capabilities when tested against oily and greasy soils.
When variations of the above formulas are made,
changing the proportion of polymer plus or minus 20% and
plus or minus 50% (to 1.5, 2.4, 3.6 and 4.5%), similar results
are obtainable but with the greater proportions of polymer
the soil release effects are better. Similarly, when such
changes are made in the builder, non ionic detergent and the
ben-tonite, polyacrylate and enzyme components, keeping the
formulas within the ranges previously given, useful products
result, of improved soil release, anti-redeposition and
comfort characteristics.
When the highly preferred polyester soil release
material is replaced by other such polyesters of molecular
weights and/or ethylene terephthalate:polyoxyethylene -lore-
phthalate ratios and/or ethylene oxide:tereph-thalate molar
ratios, such as Alkaril Chemicals, Inc. HS-15, 2056-35,
2056-36, 2056-38, 2056-39 and 2056-40, which are of lower
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molecular weights and differing hydrophile:hydrophobe ratios,
soil release properties of the detergent compositions are
no-t as good, as a rule, and neither are anti-redeposition
and "comfort" characteristics. Such is also usually the
situation with polyesters wherein the polyoxyethylene unit
weigh-t is less than 3,000, eye., 500 to 700, even a-t the
prescribed molecular weight, but such materials can be used and
may be of acceptable soil release promoting action under certain
conditions and for particular materials and soils, if -they are
applied to the base builder beads as described.
EXAMPLES 5-8
When the compositions of Examples I are made, with-
out the soil release polymer briny present, and the polymer is
added to the wash water concurrently or after the addition of
the rest of the detergent composition, either as a liquid
dispersion or in finely divided particulate form,
desirable washing and soil release results are obtainable.
Thus, when a polyethylene terephthalate - polyoxyethylene
terephthalate copolymer of a weight average molecular
weight of about 22,000, with most of the polymer being of
molecular weights in the range of 20,000 to 25,000, with the
polyoxilethylene terephthala-te component -thereof being of a
molecular weight of about 3,~00, ranging from about 3,000 -to
3,700 or ~,000, with the molar ratio of units of polyethylene
tereph-thalate to units of polyoxyethylene terephthalate in
I _
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2301-122
the polymer being about 3:1 and with the molar ratio of
ethylene oxide to phthal:ic moiety being about 22:1, and with
the percentage owe such polymer in the wash water being about
0.002~, essentially the same washing effect and accompanying
soil release promoting, anti redeposition and comfort
characteristics are obtained whether the detergent composition
containing the polymer is charged to the wash water or whether
the detergent composition less polymer is first charged,
followed by addition of the desired proportion of Alkaril* QCF
or Alkaril* QCJ, in liquid dispersion (about 16% solids,
in water) or as a particulate, preferably finely divided, solid.
The washing conditions and tests employed are the same as -those
recited in Examples 1-4, above. Similarly (to Examples 1-4)
when the less preferable soil release promoting polymers
mentioned in Examples 1-4 are added to the wash water with
of after the balance of the detergent composition components
less satisfactory but useful results may be obtained.
EXAMPLE 9
78.7 Parts by weight of the base beads described
in Example 1 (which do not contain non ionic detergent,
perfume, enzyme powder or soil release promoting polymer) are
sprayed (or otherwise blended) with 19.4 parts of Alfonic*
1214-60C non ionic detergent at an elevated temperature, as
described for Example I and Alkaril* QCF, (a solid form of
the polymer, containing no surfactant dispersing agent and
containing no more than 2% of moisture) is also mixed with
I My - 46 -
2301-1226
the base beads to produce a detergent composition containing
2.9% thereof. Clean swatches ox various types are washed in
a Whirlpool automatic washing machine of the -top loading type,
having a washing drum of 17 gallons capacity. After addition
of the swatches in a standard wash load of about eight pounds,
forty grams of the detergent composition, which has a bulk
density of about 0.5 gag are added to the wash water which
is of about 200 parts per million, as calcium carbonate, of
mixed calcium and magnesium hardness, and which is at a
temperature of about 49C. Two swatches are employed of each
of six different fabrics. The fabrics are washed, using a
normal wash cycle for the washing machine, including rinsing,
and subsequently the swatches are dried.
After drying the swatches are soiled in the centers
thereof with equal volumes (about three drops) of used dirty
motor oil and then they are rewashed with the same detergent
composition. Whiteness readings of the stained areas of the
swatches are taken, using a reflectometer. Because such
readings represent whiteness and the used motor oil is
black, the readings are directly proportional to effectiveness
of the soil release promoting action of the detergent compost-
lion containing the polyethylene - polyoxyethylene copolymer.
The same test is run for controls, in which the swatches are
first washed in the detergent composition minus the polyethyl-
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2301-1226
one - polyethylene polymer, subsequently stained with the
dirty motor oil, and then rewashed with the same control
composition. Also, whiteness readings are taken of the unsoiled
swatches, for comparisons.
Whiteness reading (Ed)
watch Material Experimental Control Unsoiled
Single knit 89 37 89
Dacron*
Double knit 87 40 88
Dacron
Dacron/cotton blend 76 60 88
(65/35)
Terry cloth* cotton 77 68 90
(14% polyester
content)
Percale* cotton 78 76 90
Diana* nylon 56 57 88
As the data show, and as is very readily visually
verifiable, oil release is virtually 100~ for the all-Dacron
swatches and is significantly better than the control for
Dacron/cotton and terry cloth cotton swatches. Little improve-
mint is noticeable for percale cotton, and Diana nylon does
not appear to have had the release of the oily soil promoted by
the preliminary washing thereof with the detergent composition
containing the polyethylene - polyoxyethylene copolymer.
However, it has been found that some nylons do have soil more
readily removed from them after treatment with the detergent
*TAM. - 48 -
2301-1226
compositions ox the foregoing examples and some cottons
also show such results. Additionally, useful anti-redeposition
effects on the various materials shown above are also
verifiable by use of the reElectometer and similar tests
wherein soil is added to the wash water and the amount
thereof depositing on the swatches during discharge of the
wash water prom the washing machine is measured.
In addition to the described soil release promoting
and anti-redeposition properties, -the washed swatches also come
paratively readily allow the transportation of moisture vapor and promote evaporation of water on the surfaces thereof,
unlike normally waxy deposits on textiles, such as qua ternary
fabric softening chemicals and other hydrophores.
Results like those given in this example are also
obtainable by use of the compositions of Examples 1-8 and
by separate additions of Alkaril QCF in particulate or aqueous
dispersion form to the washing machine. Additionally, the
compositions may be used in concentrated aqueous solution
and/or suspension, e.g., 2 to 30% (or 5 to 10%), to pretreat,
before washing, portions of clothing items that are likely
to be soiled with oily materials. Such use is to prevent
subsequent hard-to-remove soiling and is particularly
appropriate for shirt collars and cuffs, work gloves and
aprons, for example.
Many variations of the above formulas can be made,
utilizing other non ionic detergents, other builders and
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builder combinations and other soil release promoting polymers
within the invention. Also, the various proportions may be
changed within the ranges given, and useful effects of the
desired types will result. It is surprising that the present
compositions are so effective and of acceptable and practical
stability because it has been found that builders, such as
water soluble salts, have an adverse effect on polyethylene
terephthalate - polyoxyethylene tereph-thalate copolymers in
other built detergent compositions, apparently promoting
hydrolysis and deteriorations thereof which may make such
materials unsatisfactory as soil release agents, and may also
change the characteristics of the copolymers so that they make
fabrics on which they are deposited uncomfortable to the wearer.
Surprisingly, in the present compositions, although water
soluble salts may be present, apparently due to the use of
the non ionic detergent and possibly somewhat also due to the
presence of insoluble builder, such as zealot, and the use of
bentonite in some of these compositions, such interference
of the builder salt is inhibited sufficiently so as to allow
detergent compositions of useful stability to be made. Also
Good results may be attributed to the lesser proportions of
the composition that are used in the wash water, so that
the builder concentrations are lower and any undesirable
effects thereof are diminished. The nonionic-polymer
combination is also important.
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2301-1226
The particular preferred polymers, although high
in content of hydrofoil, are also satisfactorily substantive
to textiles washed with them, such as polyesters and polyester -
cotton blends, and impart soil release and comfort properties
to such fibrous materials. Thus, they have a satisfactory
balance of properties, being sufficiently hydrophobic to be
adherent to the substrates on which they are desired to be
deposited, and at the same time not being excessively hydra-
phobic. They are hydrophilic enough to promote soil release
and allow moisture transmission, and are not excessively
soluble. although it might be expected that a high hydrofoil
content of the product would make it susceptible to further
hydrolysis and inactivation in the presence of moisture, such
is not -the case with the present compositions. Finally,
the combination of non ionic detergent and soil release
agent, with the aid of the mentioned builders, results in a
product which is exceptionally effective in removing oily
and greasy soils and stains from synthetic fabrics of the
polyester and aside types, which stains are those considered
by most experts to be among the most difficult to remove
from laundry. Thus, the present detergent compositions are
significantly improved wished products and the washing
processes represent advances in the art.
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2301-1226
EXAMPLE 10
The experiments of Example 1-4 are run but the
detergent products are made from the spray dried base beads
by spraying on-to the tumbling bead surfaces a normally waxy
non ionic detergent - polymer solution comprising 20 parts of
-the non ionic detergent and 3 parts of the polymer while
the beads are being mixed in a tumbling drum or equivalent
apparatus. The tumbling drum is inclined at about 7, rotates
at about 4-20 rum (depending on the state ox spraying) and
-tumbling lasts for about 4 to 6 minutes. The solution
sprayed is at a temperature of about 50C., as are the tumbled
base beads, the spraying is through a pressure nozzle which
produces droplets in the 50 to 500 micron range, and the spray
is directed onto a falling curtain of moving base beads.
Instead of Alfonic 1214-60C, Nudely 23-6.5, 23-7, or 25 7,
and sometimes 45-11 may be substituted, at least in part. The
quantity of non ionic detergent - polymer solution sprayed is
such as to result in the Final products containing 20% of
non ionic detergent and 3% of polymer as indicated in the
formulas. The proteolytic enzyme is applied in powdered form
to result in -the desired concentration in the product, and
perfume is sprayed onto the product -to the extent ox its
desired concentration therein. The resulting detergent
compositions are of bull densities about the same as or up -to
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2301-1~26
0.1 gel higher than those of base beads but are within
the ranges previously recited. The products are attractive
and regular in appearance, and are free flowing and non-dusting.
The detergent compositions described above are
excellent heavy duty laundry detergents and are especially
useful for washing household laundry in automatic washing
machines. When employed at a concentration of about 0.05
to 0.15~, e.g., 0.06% in a top loading 17 gallon (US.)
capacity washer, in the washing of normal loads of 100%
polyester and 65% polyester 35~ cotton fabrics in home
laundry or commercial washing machines, whether of the top
loading or front loading -types, or at higher concentrations
in European type washing machines, the compositions perform
satisfactorily in the manner described and the polymer exerts
improved soil release actions after storage, compared to the
polymer in unprotected compositions wherein hydrolysis or
other degradation of the polymer can occur more readily.
When the highly preferred polyester soil release
material is replaced by other such polyesters of molecular
weights and/or ethylene terephthalate:polyoxye-thylene
terephthalate unit ratios and/or ethylene oxide:terephthalate
moiety ratios, such as Alkaril Chemicals, Inc. ISSUE,
2056-35, 2056-36, 2056-38, 2056-39 and 2056-40, which are of
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2301-1226
lower molecular weights and differing hydrophile:hydrophobe
ratios, acceptable solutions of polymer in detergent are made
but the soil release properties of the detergent compositions
are no-t as good, as a rule, and neither are anti-redeposition
and "comfort" characteristics. Such is also usually the
situation with polyesters wherein the polyoxyethylene unit
weight is less than 3,000, e.g., 500 to 700, even at the
prescribed molecular weight, but such materials can be used and
may be of acceptable soil release promoting action under
certain conditions and for particular materials and soils.
Changes in the non ionic detergent to others previously mentioned
do not seem to have detrimental effects or soil release
properties of the product. The reported good results are also
obtainable when the proportion of polymer in the spray and
in the final product is changed, as in Examples 1-4.
EXAMPLE 11
78.7 Parts by weigh-t of the base beads described in
Example 1 (which do not contain non ionic detergent, perfume,
enzyme powder or soil release promoting polymer) a-t a tempera-
lure of about 50C. are sprayed with a standard sprayer (or are otherwise blended) with lug parts of Alfonic 1214-60C non ionic
detergent and 2.9 parts of Alkaril QCF, (a solid form of the
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2301-1226
polymer, containing no surfactant dispersing agent and contain-
in no more than I of moisture) dissolved in the detergent,
which is also at a temperature of about 50C. The spraying is
of continuously moving surfaces of the beads as they are tumbled
in an inclined tumbling drum. The products made are jested,
as described in Example 9, and the results are satisfactory,
even after storage of the product.
The invention has been described with respect to
various examples and illustrations thereof but is not to be
I considered as limited to these because one of skill in the
art, with the present specification before him, will be able to
utilize substitutes and equivalents without departing from
the invention
