Note: Descriptions are shown in the official language in which they were submitted.
` ~ 2~3~26
This invention relates to detergent compositions.
More particularly, it relates to bleaching detergent compo-
sitions comprising a synthetic organic deterg~nt or mixture
of such detergents, a polyacetal carboxylate builder for
such detergent(s) and a perborate. Also within the invention
is a process for washing stained fibrous polyester materials
that had been stained with particulate soil and sebum.
The need for removing soils and stains from fibrous
materials is age-old and a multitude of compositions has been
described for accomplishing that result. One kind of prepara-
tion which has been employed to test the detersive and stain
removing activity of detergent compositions is a mixed sebum
and particulate soil, which severely stains fibrous materials
contacted with it, especially those incorporating polyester
fibers, such as polyester knits and polyester-cotton blends.
Such soil is often employed to produce an artificial ~collar
staining soil". As is well known, "collar soil n is considered
to be difficult to remove from shirt collars (and cuffs)
- 2 -
4~3~6
62301-1318
during automatic washing o~erations. It is difficult to remove
whetheL washiny is conducted at a relatively low temperature,
such as from 10 to 30C. or at higher temperature, as in accor-
dance with European practice, such as 50 to 90 or 95C.,or
higher.
Whereas once soap was the universal detergent today
almost all home laundry detergent compositions are based on one
or more synthetic organic detergents. Of such detergents the
anionic and nonionic detergents are considered to be most effec-
tive, although ampholytic or amphoteric and cationic detergentsmay also be employed. Sodium perborate has long been used in
detergent compositions for its bleaching effect. Recently poly-
acetal carboxylate builders have been employed in detergent
compositions in replacement of polyphosphate builders because
they do not contain phosphorus and accordingly have not been
thought to promote eutrophication of inland waters. Another
plus for such builders is their ready degradability in normally
acidic waste waters.
Although the main components of the present deter-
gent compositions have been employed in other such compositions,they are considered to be novel and unobvious and to possess
unexpectedly beneficial stain removing properties. Particularly
important is the greatly improved capacity of the present compo-
sitions to remove a combination of sebum and particulate stains
from polyester-containing fibrous
-- 3 --
~ ~34926
material when such material is washed in hot wash water
containing the invented detergent composition. Such effect is
even obtained when hard wash water is used.
In accordance with the present invention there is
provided a bleaching detergent composition which comprises
about 3 to 30% of a synthetic organic detergent or a mixture of
such detergents, about 4 to 50% of a polyacetal carboxylate
builder for such detergent(s) which is of a molecular weight in
the range of 3,500 to 10,000 and 10 to 50% of a perborate.
This composition, in wash water at elevated temperature, is
especially effective to remove particulate and sebum stains
from polyester fabrics. The invention also provides a process
for removing mixed particulate and sebum stains from fibrous
polyester materials which comprises washing such stained
fibrous materials in wash water at a temperature in the range
of 50 to 90C. with a detergent composition of claim 1 at a
concentration in the wash water in the range of 0.05 to 1.5% by
weight. Preferred such compositions comprise about 4 to 20% of
sodium higher alkylbenzene sulfonate wherein the higher alkyl
is of 10 to 18 carbon atoms, about 2 to 10% of a nonionic
detergent which is a condensation product of ethylene oxide and
higher fatty alcohol, wherein the higher fatty alcohol is of 10
to 18 carbon atoms and the nonionic detergent contains 3 to 20
moles of ethylene oxide per mole, about 10 to 30~ of sodium
polyacetal carboxylate builder of a calculated weight average
molecular weight in the range of 5,000 to 9,000, about 10 to
40% of sodium perborate tetrahydrate, about 3 to 20% of
moisture, including hydrate moisture which is removable at 105
C., and the balance of filler(s) and/or other builder(s) and/or
other adjuvant(s). Also within the invention is a process for
removing mixed particulate and sebum stains from
d
~2~4~26
62301-1318
fibrous polyester ma~erials which comprises washing such stained
fibrous materials in wash water at a temperature in the range of
50 to 99C. which contains a detergent composition including a
detersive proportion of a synthetic organic detergent or a mix-
ture of such detergents, a detergency building proportion of a
polyacetal carboxylate builder for such detergent(s) and a
bleaching proportion of a perborate, at a concentration of such
detergent composition in the wash water in the range of 0.05 to
1.5%.
The synthetic organic detergent which is primarily
employed for its cleaning characteristics in the present compo-
sitions will normally be an anionic detergent. Of the anionic
detergents, the sulfated and/or sulfonated lipophilic materials
having an alkyl chain of 8 to 20 carbon atoms, preferably 10 to
18 and more preferably 12 to 16, will usually be those of
choice. While various water soluble salt-forming cations may be
used to form the desired soluble sulfated and sulfonated deter-
gents, including ammonium and lower alkanolamime (such as tri-
ethanolamine), and magnesium, usually an alkali metal, such as
sodium or potassium, is employed, and very preferably such
cation will be sodium. Among the various anionic detergents
that are useful in the practice of this invention the linear
higher alkylbenzene sulfonates of 10 to 18 carbon atoms in the
alkyl chain, preferably 12 to 16 and most preferably about 12 or
13, are considered most suitable for
~ - 5 -
1 ~34~26
the practice of the invention Also, useful, among others,
are the monoglyceride sulfates, higher fatty alcohol sulfates,
sulfated polyethoxylated higher alkanols, wherein such alkan-
ols may be synthetic or natural, containing from 3 to 20 or 30
ethoxy groups per mole, paraffin sulfonates and olefin
sulfonates, in all of which compounds the alkyl group present
is of 10 to 18 carbon atoms. Some such alkyl groups may be
slightly branched but will still be of a carbon chain length
within the described range.
The nonionic detergents, which are often employed
to supplement the detersive action of the primary anionic
detergents,but in some instances may be the primary detergent(s),
are preferably normally solid materials (especially when
being incorporated in solid or particulate solid products)
and will preferably be condensation products of ethylene
oxide and higher fatty alcohol, with the higher fatty alcohol
usually being of 10 to 18 carbon atoms, preferably averaging
12 to 15 carbon atoms, e.g., about 12 to 13 carbon atoms,
and with the ethylene oxide content being within the range
of 3 to 20 moles, preferably 3 to 12 moles and more prefer-
ably 5 to 9 moles, e.g., about 6.5 or 7 moles of ethylene
oxide, per mole of fatty alcohol. Amo~g other nonionic
detergents that are also useful are the ethylene oxide
condensation products of alkyl phenols of 5 to 12 carbon
atoms in the alkyl groups, such as nonylphenol, in which the
26
ethylene oxide content is from 3 to 30 moles per mole.
Additionally, condensation products of ethylene oxide and
propylene oxide, such as those sold under the trademark
Pluronic~ may be employed, as may be various others of the
well known group of nonionic detergents.
The cationic detergPnts that may be employed,
usually in limited proportion, e.g., no more than 10% and
preferably less than 5~, are preferably di-higher alkyl,
di-lower alkyl ammonium halides, wherein the higher alkyls
10 are of 10 to 18, preferably 16 to 18 carbon atoms, the
lower alkyls are of 1 to 3, preferably 1 carbon atom(s) and
the halogens are chlorine or bromine. Among such materials
there may be mentioned distearyl dimethyl ammonium chloride,
di-tallow dimethyl ammonium chloride (wherein the alkyl is
obtained from animal fats) and dihydrogenated tallow dimethyl
ammonium bromide. However, various other such cationic
materials, including N-cetyl-ethyl morpholinium ethosulfate,
often classified as antistatic agents tthey also often have
deodorant and germicidal properties), may also be employed.
Of the amphoteric materials the Miranols may be mentioned as
examples, such as that which has been marketed under the
designation Miranol~C2M Conc. Other such detergents, includ-
ing anionic, nonionic, amphoteric and cationic detergents, are
all described in the various annual publications entitled
McCutcheon's Detergents and Emulsifiers, for example, in
that issued in 1969.
~ 284~6
62301-1318
The polyacetal carboxylate maybe considered to be that
described in U.S. patent 4,144,226 and may be made by the method
mentioned therein. A typical such product will be of the
formula
Rl - (CHO)n - R2
COOM
wherein M is selected from the group consistiny of alkali metal,
ammonium, alkyl groups of 1 to 4 carbon atoms,
tetraalkylammonium groups and alkanolamine groups, both of 1 to
4 carbon atoms in the alkyls thereof, n averages at least 4, and
Rl and R2 are any chemically stable groups which stabilize the
polymer against rapid depolymeriation in alkaline solution.
Preferably the polyacetal carboxylate will be one wherein m is
alkali metal, e.g., sodium, n is from 20 to 200, Rl is
CH3CH2O MOOC
HCO- H3C-CO-
H3C or MOOC
or a mixture thereof, R2 is
OCH2CH3
-CH
CH3
and n averages from 20 to 100, more preferably 30 to 80. The
calculated weight average molecular weights of the polymers will
desirably be within the range of 2,000 to
~ - 8 -
~ ~4~26
20,000, preferably 3,500 to 10,000 and more preferably 5,000
to 9,000, such as 7,000 to 9,000, specifically, about 8,000.
Although the preferred polyacetal carboxylates
have been described above, it is to be understood that they
may be wholly or partially replaced by other such polyacetal
carboxylates or related organic builder salts described in
various Monsanto Co. patents on such compounds, processes
for the manufacture thereof and compositions in which they
are employed. Also, the chain terminating groups described
in the various patents, especially U.S. 4,144,226, may be
utilized, providing that they have the desired stabilizing
properties, which allow the mentioned builders to be depo-
lymerized in acidic media, facilitating biodegradation
thereof in waste streams, but maintain their stability in
alkaline media, such as washing solutions.
The perborate utilized is a water soluble perborate
which is capable of releasing active bleaching oxygen in
aqueous media, such as in wash water at elevated temperature.
Such perborate is preferably an alkali metal or equivalent
salt and most preferably is sodium perborate tetrahydrate.
Usually the perborate is hydrated but that is not necessary.
Generally the hydrate is the tetrahydrate but it has been
found that the monohydrate is also useful and some perborates
with contents of water of hydration less than one mole per
2S mole may be especially useful in certain applications or
_ g _
~ 2~45~
when packaged in vapor tight containers (wherein higher
hydrates may tend to liquefy, or cake the detergent compo-
sition).
While the ordinary higher fatty acid soaps, usual-
ly the sodium soa~s, are detergents, they are not generallyconsidered to bc synthetic organic detergents, and according-
ly are not to be taken as within the group of such detergents
for the purpose of this invention. The soaps do have deter-
sive properties but may be employed for other purposes too,
such as for their foam limiting characteristics. Among the
soaps that may be utilized in the present compositions,
those of alkali metals, such as sodium, of 10 to 18 carbon
atoms and preferably highly saturated, will be preferred.
Among such are the sodium hydrogenated tallow soaps, sodium
stearate and sodium palmitate, but soaps of tallow and
mixtures of tallow with coconut oil may also be employed,
e.g., 4:1 tallow:coco soaps, as composition components.
In the compositions of the invention other builders
than the polyacetal carboxylate may also be present although
such are not necessary. Often it will be desired to avoid
the presence of phosphorus in the detergent compositions so the
polyphosphates, which have been the builders of choice in
the detergent art for many years (especially pentasodium tri-
polyphosphate), will preferably be omitted from the present
formulations. Still, in some instances, they may be present,
-- 10 --
4~X~i
at least in relatively small proportions, e.g., up to 5 or
10%. Among builders other than polyphosphates, such as
sodium tripolyphosphate and tetrasodium pyrophosphate,
those which may be desirably incorporated in the present
compositions to supplement the building action of the poly-
acetal carboxylate include sodium carbonate, sodium bi-
carbonate, sodium sesquicarbonate, sodium silicate, zeolites,
e.g., Zeolite A, NTA, sodium citrate, sodium gluconate,
borax, other borates, and other builders known in the deter-
gent art.
Fillers may be present, such as sodium sulfate andsodium chloride, to add bulk to the product when that is
considered to be desirable. In liquid compositions, which
should usually be employed soon after making, solvents or
extenders may be used, such as water, ethanol and
isopropanol.
Among the various adjuvants that may be employed
are colorants, such as dyes and pigments, perfumes, enzymes,
stabilizers, activators (especially activators for causing
active oxygen release from perborates), fluorescent bright-
eners, buffers, fungicides, germicides and flow promoting
agents. Also included among adjuvants, unless in other
classes previously mentioned, are various additional components
or impurities present with other ingredients. For example,
it is known that sodium carbonate and water are often present
4~
with polyacetal carboxylate in Builder U, the product which
is the present source of polyacetal carboxylate.
Moisture will usually be present in the invented
compositions, either as free moisture or in one or more
hydrates. While moisture is not an essential component of
these bleaching detergent compositions it will normally be
present due to the use of water in manufacturing, and it
may help to solubilize other composition components and bind them.
The proportions of components of the invented
compositions given below are those for particulate products,
which are usually of particle sizes in the 8 or lO to 100 or
140 sieve (or mesh) range, U.5. Sieve Series. However, such
proportions also apply to other olid forms, such as bars or
cakes, more fine]y divided or coarser powders, granular
lS compositions and agglomerates, and also to liquid prepara-
tions, althouqh because of their relatively low stability
aqueous liquid preparations should be used relatively soon
after manufacture. Also, while the proportions of all the
components except water may be about the same in liquid
preparations, such products are often much more dilute, 80
that the proportion of water or other solvent or a mixture
of solvents present may be much greater. In some aspects of
the invention the components may be added directly to the
wash water, in which case it may be considered that the
detergent composition is the wash water containing the
various active and other components.
- 12 -
4~
In the particulate solid and other solid detergent
compositions of this invention the total proportion of
detergent present will normally be from 5 to 40%, more
preferably from 10 to 25% and most preferably about 12%.
Such detergent will desirably include either sulfated or
sulfonated anionic detergent or nonionic detergent but pre-
ferably will include both such detergents. The proportion
of anionic detergent present will usually be from 3 to 30%,
preferably 4 to 20% and more preferably 4 to 10%, e.g.,
about 8%, and the proportion of nonionic detergent will be
about 2 to 25%, preferably 2 to 10% and more preferably 2 to
6%. The proportion of polyacetal carboxylate builder will
usually be within the range of 4 to 50%, preferably 10 to
30%, and more preferably 10 to 25%, e.g., 18~. The perborate
content is normally in the range of 10 to 50%, preferably
being 10 to 40% and more preferably 15 to 30%, e.g., 22%,
which percentages are on the basis of sodium perborate
tetrahydrate and may be modified accordingly when the anhydrous
salt or a different hydrate is employed. The proportion of
soap, when it is present, will usually be in the range of 1
to 10%, preferably 2 to 6%, and the percentage of moisture
will normally be from 3 to 20%, preferably 5 to 15%, e.g., about
10%. Such percentages include moisture in hydrate form that
is released during heating for two hours at 105C. (the
standard moisture analyzer method). The proportions of
- 13 -
~ 284'326
other components, such as fillers,will normally be limited
to no more than 40% and usually will be in the range of 0 to
30% or 5 to 20%. Similarly contents of builders other than
the polyacetal carboxylate will be limited, generally being
less than 25%, such as 3 to 20% or 5 to 15%, but often no
such supplemental builders will be present. The total
adjuvar.t content will usually not exceed 10% or 20~, and
preferably will be less than 5%, with the contents of
individual adjuvants generally not exceeding 3% or 5%, and
preferably being less than 1 or 2%. For example, sodium carboxy-
methyl cellulose, which is a desirable antiredeposition
agent, will usually be present within the range of 0.~ to
3%, preferably 0.5 to 2%, e.g., 1%.
In preferred forms of the invention, particulate
solid compositions of particle sizes such as those previous-
ly described, it is often preferred to spray dry as much of
the formulation as feasible so as to obtain substantially
uniformly shaped globular particles. Because the perborate
i6 heat-unstable it will normally be post-added to the rest
of the composition. Of course, to prevent segregation
during shipping and storage of the final product it is
desirable that the perborate be of shape and particle sizes
like those of the rest of the composition. The polyacetal
carboxylate may sometimes be spray dried with the detergent
composition providing that care is exercised to prevent it
- 14 -
9~6
from being decomposed by heat. However, it may also be
post-added, and again the particle sizes for post-adding are
desirably the same as those previously mentioned, to avoid
product component segregations. In an alternative method of
manufacture the various components, in finely divided form,
may be merely mixed together. Also, when the initial
particle sizes of the components are less than desired, such
as in the 160 to 325 mesh range, particles thereof may be
agglomerated to the desired size, sometimes with the aid of
agglomerating agents, such as a dilute aqueous solution of
sodium silicate, and at other times with only water to
assist in agglomeration.
When an anionic detergent is the primary detergent
of the desired composition it may be spray dried with fillers,
lS such as sodium sulfate, builders, such as sodium carbonate,
sodium bicarbonate, borax and sodium silicate, and adjuvants,
such as fluorescent brighteners, pigments and dyes, and may
be spray dried in the normal manner, utilizing a conventional
countercurrent or concurrent spray drying tower with drying
20 air entering at about 200 to 600C. (preferably 150 to 300
or 350C. when polyacetal carboxylate is present). Then
the polyacetal carboxylate and perborate may be admixed, in
either order or conjointly, or the perborate and polyacetal
carboxylate may be pre-blended and then mixed with the spray
dried beads. When a relatively small proportion of nonionic
- 15 -
detergent is to be present with the anionic detergent it may
be spray dried with such anionic detergent, fillers, etc.,
and stable amphoteric and cationic materials that are to be
present can also be incorporated in the crutcher and then
spray dried with the anionic detergent. However, when more
than about 4 or 5~ ~sometimes more than 2~) of nonionic
detergent is present in the formula any additional proportion
will usually be post-added, as by spraying onto tumbling
particles of detergent beads or base beads. Such base beads
may be made from any builders, fillers and stable adjuvants
of the final product. Then the polyacetal carboxylate and
perborate may be post-added. In some instances the poly-
acetal carboxylate may be dispersed and/or dissolved in the
nonionic detergent, which is heated so as to be in liquid
state (or may be dissolved in a solvent) and the combination
oS nonionic detergent and polyacetal carboxylate may be
sprayed onto the detergent beads or base beads, followed by
addition of perborate. Desirably, the particulate material
made will be of particle sizes in the ~ to 120 or 10 to 100
mesh range and the manufacturing process will be designed
accoxdingly. ~owever, screening may be employed to remove
under- and over-sized particles, which may be reworked,
ground, agglomerated or otherwise processed to sizes desired.
To manufacture the present products into bar, cake
or briquette form the compositions may be extruded, pressed
- 16 -
~ ~84~26
62301-1318
or molded to shape in known manners. To convert them to liquid
preparations the components may be dissolved and/or dispersed in
liquid media, such as water and/or suitable solvent(s).
To practice the stain removing process of the invention the
described composition may be added to "wash water" or the vari-
ous components may be so added. ~ormally the concentration of
the compositions employed will be in the range of 0.05 or 0.1 to
1.0 or 1.5~, preferably 0~1 to 1.3%, and more preferably 0.15 to
1.1 or 1.2%. Higher concentrations, as from 1.0 to 1.5% or
more, are often employed in machine washing according to
European practice, which utilizes high temperature wash water,
in which the perborate releases active bleaching oxygen.
Usually the washing temperature in America will be in the range
of 10 to 55C., often being from 10 to 30C., compared to 60 to
- 99, often 70 to 90 or 95C.,in Europe. In American practice
lower concentrations, such as from 0.05 to 0.2~, often prefer-
ably about 0.07 to 0.15~, of the composition are employed.
Following American practice perborate oxygen is not released to
the same extent because the washing temperature is lower. Con-
sequently any bleaching effect is not as great as when higher
wash temperature are used, unless an activator is also present
to assist in the release of active oxygen from the perborate.
Various such activators are known for this purpose and may be
employed to adapt the process invention to American practice.
Among such activators are those known as TAED (tetraacetylethy-
lene diamine, acyloxybenzene, sulfonates, such as described in
U.S. Patent 4,412,934, and TAGU.
- 17 -
~ X~34~326
62301-1318
In the washing or stain removing operation convention-
al washing machines will be employed, such as GE automatic
washers (top loading), following the American practice, and
Miele machines, following European practice. While it is con-
sidered that the present compositions operate better than con-
trols utilizing sodium tripolyphosphate in place of polyacetal
carboxylate, whether washing is at high or low temperatures,
providing that equivalent proportions of active oxygen are
released from the perborate, it is often preferred to follow the
European practice, which does not require the presence of an
accelerator to promote the release of active oxygen from the
perborate. Various hardnesses of water may be utilized and
while it might be expected that the softer the water the better
the stain removal, unexpectedly it has been found that even
under hard water conditions the present compositions and stain
removing processes are superior to controls wherein pentasodium
tripolyphosphate is employed instead of the polyacetal carboxy-
late. This improved stain removing capacity is most pronounced
at elevated temperatures (60 to 90C.) when the stain is a very
critical stain, usually found in normal laundry, a combination
of particulate and sebum stains, such as may be found on shirt
collars and cuffs. The good effect in removing such stains is
obtained even when hard water is used, such as that of hard-
nesses that are quite high, such as in the 250 - 350 p.p.m.
range, as
Xl - 18 -
~ ~4~
CaCO3. In addition to better removal of such stains, which
is even more evident at 90C. than at 60C., it is found
that the invented compositions and processes result in
significant improvements with respect to removals of various
other typical stains too. Surprisingly then, the present
compositions, incorporating a builder which is stable during
washing and stain treatment but is degradable in normally
acidic waste waters, and omitting one of the best previously
known builders, sodium tripolyphosphate, in~combination
with synthetic organic detergent (especially a mixture of
anionic and nonionic detergents) and perborate bleach, give
superior stain removal, which is apparently attributable to
the particular unique combination of components employed.
Such effect is obtained even in very hard water, which is
unexpected in view of the excellent sequestering activity of
the sodium tripolyphosphate builder and its known stability
and widespread utility in washing and stain removal opera-
tions.
The following examples illustrate but do not limit
the invention. Unless it is otherwise indicated, all parts
are by weight and all temperatures are in C. in these
examples, elsewhere in the specification, and in the claims.
-- 19 --
128~926
EXAMPLE 1
Component Percent
* Sodium linear tridecylbenzene sulfonate 8.0
~ * Nonionic detergent lNeodol 25-7, a condensation 4.0 product of hiqher fatty alcohols averaging 12 to 15
carbon atoms, and 7 moles of ethylene oxide per
mole of fatty alcohol, obtainable from Shell
Chemical Co.)
* Sodium hydrogenated tallow soap 4.0
* Sodium carboxymethyl cellulose 1.0
Sodium perborate tetrahydrate 22.0
Builder U (79.7% of sodium polyacetal carboxylate, of 22.0
calculated weight average molecular weight of
about 8,000, obtained from Monsanto Co.)
* Filler (sodium sulfate, anhydrous) 29.0
Moisture 10.0
100. 0
* in spray dried beads
A stain removing detergent composition of the
above formula is made by spray drying a crutcher mix, contain-
ing about 55% of solids and 45% of water (city water of
hardness of about 100 p.p.m., as calcium carbonate) and at
a temperature of about 50C., into a countercurrent spray
drying tower, wherein it is dried to a moisture content of
about 10%. The tower inlet air is at about 450C. and at
the outlet from the tower such air temperature has been
reduced to about 150C. The spray dried beads resulting are
~ rr~dt ~1ar~
- 20 -
~.~849~6 62301-1318
of particle sizes in the range of No's. 10 to 100, U.S. Sieve
Series. With such beads there are admixed in an inclined tumb-
ling drum the sodium perborate tetrahydrate and Builder U, also
of particLe sizes in the 10 to 100 sieve range. When the compo-
nent materials are supplied as finer powders and none is spray
dried they are (or may be) agglomerated to the desired sizes,
alone or together. Such polyacetal carboxylate - perborate
agglomerates may be of pro- portions in the range of 1:5 to 5:1
and may contain from 0.1 to 5% of sodium silicate (Na2O:SiO2 =
1:1.6 to 1:3), as a binder.
The product obtained is tested for stain removing
action, utilizing a Miele*/multi-stain light reflecting
procedure wherein delta Rd's are measured for washed
experimental and control swatches. In such procedure the
experimental composition and control detergent composition
(containing trisodium polyphosphate instead of Builder U) are
separately charged to a Miele washing machine at a concentration
of about 1.1~ (225 grams per 20 liters of wash water) at 60C.,
with water over 200 p.p.m. (300 p.p.m) hardness as calcium
carbonate, and having a hardness of a 4:1 ratio of calcium ion
to magnesium ion. The test specimens employed are of different
materials and have been stained with different stains. A
plurality of test cloths is employed for each combination of
cloth and stain and average reflectance readings from the cloths
are taken after normal washings and
*Trade-mark
~ - 21 -
~Z84~26
dryings with the experimental composition of this example
and are compared to those for the control detergent composi-
tion, wherein 22~ of sodium tripolyphosphate is present
instead of the Builder U. Such procedures are repeated at
90~C. with the exception that the washing procedure is
modified so that half of the detergent composition and half
of the control are employed in pre-wash steps and the other
halves are employed in the main washings.
By the test method described, which is considered
to be a standard for testing stain removal properties of
detergent compositions, it is found that the invented compo-
sition of this example and use of the washing process of
this example result in significant improvements with respect
to removals of various typical stains found on items to be
laundered, including Spangler sebum/particulate stain on
Dacro~ double knit material, liquid makeup on cotton percale,
on Qiana jersey and on Dacron double knit materials, Bico9
black pen ink on Dacron-cotton blend material and French
dressing on a Dacron double knit, at 60C., and Spangler
sebum/particulate stain on Dacron double knit material,
liquid makeup on cotton percale, on Dacron-cotton blend and
on Qiana jersey, and colored shortening on Dacron double
knit,at 90C. The invented compositions and processes were
found to be inferior in stain removal to tripolyphosphate-
containing controls only for brewed tea stain on polyester/cotton blend and for barbeque sauce on Dacron double knit
fJ D~ R 1~,
- 22 -
4~2~;
(both at 60C.), and for liquid makeup on Dacron double knit
and for French dressing on Dacron double knit (both at
90C. ) .
Results like those described above are also obtain-
able when the experimental formula is varied by increasing
the alkylbenzene sulfonate content to 16%, omitting the
nonionic detergent and soap, and replacing the 29~ of sodium
sulfate with a third each of sodium bicarbonate, sodium
carbonate and sodium silicate of Na20:5iO2 ratio of about
1:2.4. Similarly, such second formula may be varied by
utilizing a mixture of equal parts of the alkylbenzene
sulfonate and sodium lauryl sulfate (totalling 16%) or by
omitting the alkylbenzene sulfonate and replacing it with
~ post-sprayed nonionic detergent (Neodol 25-7 or Neodol 23-
6.5), after which the sodium perborate and Builder U are
admixed with the base beads containing nonionic detergent.
In such instances the improved stain removing property,
attributable to the combination of polyacetal carboxylate
and perborate in the present formulations, will also be
obtained. Instead of the mentioned nonionic detergents
other such detergents may be substituted, including the
condensation products of ethylene oxide and nonylphenol, as
previously described, Pluronics, e.g., F-68, and Neodol 45-
11, and mixtures thereof containing two to four components.
Other variations in this example may be made, as
~ -r R ~ D~
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~ 3~ ~
by utilizing other builders and fillers than those employed,
including small proportions, e.g., 1 to 10 or 2 to 5% of
amphoteric and/or cationic detergents (the cationic detergents
may be employed as antistatic agents) in the formulas,
and/or by varying the proportions of the indicated constituents
+10 and +25%, while maintaining them within their respective
ranges. Also, the conditions of manufacturing may be varied,
as by spray drying essentially all the components (usually
except perborate, perfume and enzymes) together, using mild
conditions lto prevent degradation of the Builder U).
EXAMPLE 2
The formulas of the product of Example 1 are modified
by use of a Builder U of calculated weight average molecular
weight of about 5,250, which is 83~ of sodium polyacetal
carboxylate polymer. Such formulations, when made by the
methods described in Example 1, are of improved stain removing
properties, compared to controls containing sodium tripoly-
phosphate instead of the Builder U polymer, and the experi-
mental products exhibit stain removing capabilities like
those of the formulations of Example 1. Such is also the
case when an equivalent proportion of perborate monohydrate
is employed instead of the tetrahydrate,with the difference
being made up by inert builder (Na2SO4). The described
products are also producible in paste, liquid and bar or
2S cake forms by conventional means, as mentioned previously.
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J ~34~2~i
EXAMPLE 3
In the primary formula of Example 1 the sodium
linear tridecylbenzene sulfonate is replaced by sodium
dodecylbenzene sulfonate, sodium paraffin sulfonate, sodium
olefin sulfonate (averaging about 16 carbon atoms), sodium
lauryl sulfate and sodium monoglyceride sulfate, respectively.
When tested by the method described in Example 1 such products
are also significantly superior for the removal of stains
from laundry, compared to various controls, utilizing other
builders instead of the sodium polyacetal carboxylate, among
which builders is included pentasodium tripolyphosphate.
In variations of such formulas the composition is
modified to include an activating proportion, e.g., about 1%,
of TAED (with the sodium sulfate content being correspondingly
diminished), with such activator being post-added to the
composition. Upon testing in the manner described in Example
1 for use at 60C., but lowering the temperature of the wash
water to 30~C., in accordance with American practice, and
using a G.E. top-loading washing machine, improved stain
removing results are obtained, compared to a control containing
sodium tripolyphosphate instead of Builder U. Such is the
case with polyacetal carboxylate active polymers of molecular
weights of about-5,000 and about 8,00g. However, it is
considered that best stain removals are obtained by the
primary method of Example 1, which may be modified to have
present other polyacetal carboxylates of calculated weight
* Monsanto Lot No. 2547312 (M.W. = 5,250)
~* Monsanto Lot No. 2538422 (M.W. = 8,034)
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~ ~34~i~6
average molecular weights in the given ranges.
In a modification of this example (Examples l and
2 may also be so modified) a liquid product or slurry is
made by replacing the sodium sulfate or other fillers and/or
builders (except polyacetal carboxylate) in the various
formulas with water. Such products, when made at the same
active ingredient concentrations as those of these examples,
are also effective stain removers. In still another varia-
tion of the invention, the various components of the compo-
sition may be separately added to the wash water to obtainthe desired results. Of course, for final commercial
products adjuvants will also be present, for example, 0.5%
of perfume, 1% of proteolytic enzyme, 2% of fluorescent
brightener composition, 0.2% of colorant, such as Polar
Brilliant Blue dye and/or Ultramarine Blue pigment for
making a blue product, and 3~ of flow improving agent, such
as magnesium silicate hydrate, if thought to be desirable.
It is not considered that employment of any such adjuvants
will significantly adversely affect the desirable properties
of the invented compositions, or the operations of the
invented processes.
From the foregoing description and the examples of
compositions and processes within the present invention it
is apparent that the combination of polyacetal carboxylate
and perborate in the present compositions leads to surpris-
ingly improved stain removing products and methods, especially
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~284926
with respect to hard to remove combination sebum and partic-
ulate stains on polyesters, even when the washing medium is
a hard water. It is especially surprising that such results
ehould be obtained, considering that sodium tripolyphosphate
has been the most effective detergent builder employed in
the past, and also considering that the proportion of active
polyacetal carboxylate polymer employed is less than the
proportion of polyphosphate in the control compositions.
Thus, it is thought that that a significant advance in the
stain removing and cleaning arts has been made by the pre-
sent invention.
The invention has been described with respect to
various illustrations and embodiments thereof but it is not
to be limited to these because it will be evident that one
of skill in the art, with the present specification before him or
her, will be able to utilize equivalents and substitutes
without departing from the invention.
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