Note: Descriptions are shown in the official language in which they were submitted.
123~6~l
This invention relates to a built synthetic organic
detergent composition. More particularly, it relates to such
a composition containing a building proportion of a lower
molecular weight polyacetal carboxylate builder for the
synthetic organic detergent. The invention also includes
prowesses for washing soiled fibrous materials, in which
processes the described compositions or the components
thereof are utilized.
Synthetic organic detergent compositions in which
anionic and/or non ionic detergents have been employed as the
detersive components and organic or inorganic builder salts
have been present have long been employed commercially.
Among the synthetic organic detergents those which have
generally been preferred in the past have been the anionic
detergents but non ionic detergent compositions and mixed
anionic-nonionic products have been successfully marketed,
too. Various organic and inorganic builder salts have been
included in commercial home laundry detergent compositions
~L239~
and of these until very recently sodium tripolyphosphate was
almost invariably the most preferred. Such polyphosphate is
an excellent builder which is safe to the consumer and is
reasonably priced, while yet being extremely effective for
its intended building purpose. However, in recent years
phosphorus has been blamed for inland water pollution due to
eutrophication and for that reason its use in detergent
compositions has been controlled, restricted or prohibited
in various political jurisdictions. Accordingly, efforts
have been made to manufacture detergent compositions that
are phosphate-free and which yet are effective heavy duty
detergents.
Among non-phosphate compounds that have been
suggested for use as builders in detergent compositions are
the polyacetal carboxylates. Such compounds have been
described in various U.S. and foreign patents. For example,
detailed descriptions of them have been given in U.S. patents
4,144,226 and 4,146,495, both assigned to Monsanto Company.
Normally, according to such patents, the molecular weights
of such materials will be in the range of 1,000 to 40,000 or
more, preferably 1,000 to 20,000 and more preferably 5,000
to 10,000. However, while the anionic and non ionic synthetic
organic detergents and the polyacetal carboxylates of this
invention have been disclosed in the prior art as detergent
composition components, such art has not suggested and does
-- 3 --
I
not make obvious the employment of a combination of synthetic
organic detergent having an ethics group therein with a
polyacetal carboxylate, the molecular weight of which is in
a comparative narrow low range. Such compositions, it has
been found by applicant, exert improved cleaning effects, better
removing hard to remove soils and stains from a variety of
fibrous substrate materials during cold water washing in
medium hardness water, compared to similar compositions
including a polyacetal carboxylate of higher molecular
weight, and are also superior to control compositions in
which the polyacetal carboxylate is replaced by a polyp
phosphate builder.
In accordance with the present invention a built
synthetic organic detergent composition, especially useful
for washing laundry in cold water of a hardness in the range
of 50 to 150 ppm. as calcium carbonate, comprises from 5
to 30% of a synthetic organic detergent selected from the
group consisting of anionic and non ionic synthetic organic
detergents and mixtures thereof, which detergent(s) contain(s)
at least one ethics group per molecule, 5 to 95~ of polyacetal
carboxylate builder of calculated weight average molecular
weight in the range of 3,000 to 6,000, and the balance of
such composition, if any, of adjutant and/or filler(s)
and/or builder(s) and/or delineate. Preferably, the
anionic detergent is a sulfated higher fatty alcohol
Lowe
ethoxylate and the non ionic detergent is a condensation
product of ethylene oxide and a higher fatty alcohol. While
particulate detergent compositions are preferred such compost-
lions can be of other types too, including bars, cakes,
liquids, pastes and powders. When particulate products are
made various processes may be employed, such as spray drying,
spray cooling, agglomeration, granulation, comminution and
compaction.
Also included within the invention are processes
for washing soiled fibrous materials by utilizing the
described compositions to wash the soiled materials in wash
waters of harnesses in the 50 to 150 ppm. range and at
temperatures in the range of 10 to 70C., preferably 10 to
30C. Additionally, processes for washing laundry with the
synthetic organic detergent and polyacetal carboxylate
components of the described compositions are parts of this
invention.
Although cat ionic and/or amphoteric detergents may
be included in minor proportions in the compositions of the
present invention, they will normally be limited to a 10~
total thereof and preferably will be held to less than 5%,
if present, The primary detergents employed in accordance
with the present invention are anionic and/or non ionic. Of
the anionic detergents the sulfated and/or sulfonated
lipophilic materials having an alkyd chain of 8 to 20 carbon
~23~56~L
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 detergents, including ammonium and
lower alkanolamine (such as triethanolamine), 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 are the linear higher alkylbenzene
sulfonates, the monoglyceride sulfates, higher fatty alcohol
sulfates, paraffin sulfonates and olefin sulfonates. In all
of such compounds the alkyd (or aureole, for the monoglyceride
sulfates) group present will be in the range of 10 or 12
to 18 carbon atoms. While some such alkyd groups may include
branching they will still be of a carbon chain length within
the described range. Although the mentioned anionic detergents
are useful in the practice of the invention that which is
considered most useful and most effective, in combination
with the polyacetal carboxylate builder, is an anionic
detergent which includes an ethics group. Among these the
most preferred are the sulfated polyethoxylated higher
alkanols, wherein such alkanols may be synthetic or natural,
and which contain from 3 to 20 or 30 ethics groups per mole.
Preferably, such detergents are alkali metal salts, e.g.,
sodium salts, the higher fatty alcohols thereof are of 12
-- 6 --
1~;?3956~l
Jo 18 carbon atoms and the detergents contain from 3 to 12,
preferably 3 to 7, e.g., 3 or 5 molar proportions of ethics
groups per mole.
The non ionic detergents, which may be employed as
the primary detergents in place of the anionic detergents,
or may be used with the avionics, are preferably normally
solid materials (especially when being incorporated in solid
or particulate solid products) and will preferably be condemn-
station 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 preferably 5 to 9 moles,
e.g., about 6.5 to 7 moles of ethylene oxide per mole of
fatty alcohol. Among other non ionic detergents that are
also useful are the ethylene oxide condensation products of
alkyd phenols of 5 to 12 carbon atoms in the alkyd groups,
such as nonylphenol, in which the 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 non ionic
detergents in which a lipophilic group, such as higher alkyd,
alkylphenyl, polyoxy-lower alkaline, e.g., polyoxypropylene,
is joined to a polyoxyethyleneethanol by reaction with
ethylene oxide.
356~l.
The polyacetal carboxylate may be considered to be
of the type that is 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
Al - (Sheehan R2
COO
wherein M is selected from the group consisting of alkali
metal, ammonium, alkyd groups of 1 to 4 carbon atoms, twitter
alkylammonium groups and alkanolamine groups, both of 1 to 4
carbon atoms in the alkyds thereof, n averages at least 6,
and Al and R2 are any chemically stable groups which stabilize
the polymer against rapid depolymerization in alkaline soul-
lion. Preferably the polyacetal carboxylate will be one
wherein M is alkali metal, e.g., sodium, Al is
CH3CH2O MOO
HO- or H3C-CO-
H3C MOO
or a mixture thereof, R2 is
0,CH2CH3
-OH
SHEA
and n averages from 15 to 120, more preferably 40 to 70.
The calculated weight average molecular weights of the
polymers will normally be within the range of 3,000 to
-- 8 --
~.3956~
6,000, preferably 4,000 to 6,000 and more preferably 4,500
to swish as about 5,250.
though the preferred polyacetal carboxylates
have been described above, it is to be understood that they
may be wholly or partially replaced at least in part 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 compost-
tions,if of the same molecular weights. The various chain
terminating groups described in the various patents, especially
U.S. ~,144,226, may be utilized, providing that they have
the desired stabilizing properties, which allow the mentioned
builders to be depolymerized in acidic media, facilitating
biodegradation thereof in waste streams, but maintain their
stability in alkaline media, such as washing solutions.
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
tripolyphosphate), will preferably be omitted from the
present formulations. Still, in some instances, they may be
present, at least in relatively small proportions, e.g., up
to 5 or 10%. Among builders other than polyphosphates such
~2~S6~
as sodium tripolyphosphate and tetrasodium pyrophosphate,
those which may be desirably incorporated in the present
compositions to supplement the building action of the polyp
acutely carboxylate include sodium carbonate, sodium bit
carbonate, sodium sesquicarbonate, sodium silicate, zeolites,e.g., Zealot A, NAT, sodium citrate, sodium gluconate,
borax, other borate, and other builders known in the deter-
gent art. Fillers may be present, such as sodium sulfate
and sodium 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, delineates, such
as solvents, dispersants, extenders and antifreezes, may be
present, as well as adjutants, such as buffers, thickeners
and stabilizers. The usual delineates include water, ethanol,
lo isopropanoland propylene glycol, and the adjutants include
gums, clays, polymers, and salts.
Among the various other adjutants that may be
employed in particulate compositions (but some can also be
used in liquids) are colorants, such as dyes and pigments,
perfumes, enzymes, stabilizers, activators (especially
activators for causing active oxygen release from perorate,
if present), fluorescent brighteners, fungicides, germicides
and flow promoting agents. Also included among adjutants,
unless in other classes previously mentioned, are various
additional components or impurities that may be present with
other ingredients. For example, it is known that sodium
carbonate and water are often present with polyacetal
carboxylate in Builder U, the product which it the present
source of polyacetal carboxylate.
-- 10 --
~Z3956~
Moisture will usually be present in the invented
solid (including particulate) compositions, either as free
moisture or in one or more hydrates. While moisture is not
an essential component of these improved detergent compost-
lions it will normally be present due to the use of water in manufacturing, and it may help to syllables other compost-
lion components and bind them together, as is usually desired.
The proportion of total synthetic organic detergent
may be a detersive proportion up to 40% of the present
compositions but normally will be within the range of 5 to
30%, preferably 5 to 25% and more preferably 10 to 20%,
e.g., about 15%. Such proportions normally will be for either
the sodium higher fatty alcohol polyethoxylate sulfate
anionic detergent, the non ionic detergent which is a condemn
station product of higher fatty alcohol and ethylene oxide or
a combination of the two. At times when combinations of
such two detergents are employed the proportions thereof
will generally be within the range of ratios of 1:5 to 5:1,
preferably 1:3 to 3:1 and more preferably 1:2 to 2:1, e.g.,
1:1. In such compositions the proportion of higher fatty
alcohol polyethoxylate sulfate will usually be in the range
of 2.5 to 27.5%, preferably 3 to 12% and more preferably 5
to 10~. The percentages of higher fatty alcohol polyoxy-
ethylene condensation product in such compositions will be
the complements of the percentages of such anionic detergent,
~;~395~;1
with such non ionic detergent percentages being in the same
ranges as given previously for the anionic detergent,
with the ratio of the anionic detergent to the non ionic
detergent being within the range of ratios mentioned, and
with the total of anionic and non ionic detergents being deter-
size proportions in the ranges previously given.
The proportion of polyacetal carboxylate builder
is a building proportion (or is such a proportion in combine-
lion with any other builders that may be present). The
polyacetal carboxylate builder may be from 5 to 95% of the
composition, preferably being from 10 to 50% thereof, more
preferably 15 to 40~, and most preferably about 20 to 30%
thereof, e.g., about 25~. Such concentration is on the
basis of the active polymer, which normally constitutes
about 80 to 87~ or available sources of the polyacetal
carboxylate builders, being 83~ of Lot No. 2547312 of
Builder U (obtained from Monsanto Company), which is of a
calculated weight average molecular weight of 5,250, and
which Cantonese of sodium carbonate, with the balance
being mostly water.
The ratio of synthetic organic detergent to polyp
acutely carboxylate will normally will be in the range of
1:10 to 2:1, preferably being 1:5 to 1:1, more preferably
being 1:3 to 4:5, e.g., 5:8. Such ratios include detergents
other than those containing at least one ethics per molecule,
- 12 -
~23~5~
but such, if present, will be only a minor part, preferably
less than 1/5 and more preferably less than 1/10 of the total
detergent.
The other components of the present compositions,
S in addition to the synthetic organic detergent(s) and sodium
polyacetal carboxylate(s),will be other builder(s) and/or
filler(s) and/or solvent(s) and/or delineate and/or dispel-
sent and/or adjutant. While technically, only the
detergent and polyacetal carboxylate are required components
of the invention in its broadest aspects, normally other
materials will also be present for their supplementing
properties. Any supplementing builder materials that may be
present will normally be limited to 50~, preferably being
from 2 or 3 to 40~ and more preferably from 5 to 30%. Among
the move preferred of the supplementing builders are sodium
carbonate, sodium bicarbonate, Zealot A (but other zealots
may also be employed), sodium silicate of Nash ratio
in the range of 1:1.6 to 1:3.0, preferably 1:2.0 to 1:2.6,
and in some cases (although not preferred), polyphosphates,
such as sodium ~ripolyphosphate and tetrasodium pyrophosphate.
The proportions of such individual components will usually
be limited to 30% and preferably will be no more than 20%.
The proportion of sodium carbonate which may be employed is
more preferably 5 to land the quantity of sodium silicate
is more preferably from 3 to 12%. If phosphates are present
the proportions thereof will preferably be limited to 10% or less.
- 13 -
~,2395~;1
The content of filler in the present formulations
will normally be no more than 70~, preferably being in the
range of 10 to 60~, more preferably 10 to 40%. While such
filler is usually sodium sulfate, it may also include a minor
proportion, less than half thereof, of other filler materials,
such as sodium chloride.
Adjutants in the invented compositions wit]. normal-
lye total no more than 20% and preferably will not exceed 10%
with the exception that when bleaching material such as
sodium perorate, is employ edit can constitute up to about
30~ of the product), and preferably the total adjutant
content will be less than Wyeth individual adjuvant.contents
generally not exceeding I or 5%, and preferably individually
being less than 1 or 2%. Thus, if a sodium soap of a higher
fatty acid (10 to I carbon atoms) is present, (for its
foam diminishing property) it might be desired to employ 1
to 4% thereof and if sodium carboxymethyl cellulose is
utilized (as an anti redeposition agent), the proportion
thereof may be in the range of 0.3 to I preferably being
about I In liquid preparations highly porous silica
products, such as those sold under the trade name Cab-O-Sil~,
may be employed in proportions from 0.5 to 5% to help to
maintain the polyacetal carboxylate suspended, and from 1 to
5% of hydrotrope(s), such as sodium zillion sulfonate, may be
present to promote physical stability and uniformity of the
- 14 -
Lowe
product. The moisture contents of the invented products
will usually be from 3 to 20~, preferably 5 to 15% and more
preferably 5 to 12%, for solid or particulate solid products,
and for liquids may increase to proportions in the range of
20 to 90~, preferably 25 to 70~ and more preferably 30 to
60%. Part of the water content of liquid (or paste) prepare-
lions may be replaced by other solvents, with the percentages
of such other solvents (such as ethanol) in the final product
normally being in the range of 2 to 30%, preferably 5 to
20%, if present. Such supplementary solvents may help to
syllables composition components and can be used to control
product viscosity.
he manufacture of the invented compositions may
be conducted in any suitable conventional manner, whether
solid or liquid products are being made. For liquid products
the delineate (solvent or dispersant) may have the various
components added thereto, normally preferably with a hydrotrope
or other dispersing agent for the polyacetal carboxylate and
any other insoluble present, being in the liquid medium when
the various components are admixed therewith. Admixing may
be sequential or simultaneous with sequential admixing
being the usual practice. The order of additions that is followed
normally will not matter significantly but usually any
colorants and perfumes will be admixed near the end of the
procedure. Often too, viscosity adjusting materials will be
-- 15 --
~L239~;6~
added after other components. In some instances it may be
desirable to withhold some of the solvent for final addition,
whereby a final thinning of the mix may be obtained, when
desired. Various types of mixers may be employed and in
some instances utilization of homogenizing mixers may be
preferred. Instead of the liquid form, with viscosities in
the readily plowable range, dispensable through a narrow-
necked bottle in a practical manner, non-flowing pastes may
be produced, which normally will include greater proportions
of a thickening agent and often lesser proportions of
solvent or delineate.
To make the preferred particulate solid compositions,
which will usually be of particle sizes in the 8 to 120 or
10 to 100 sieve (U.S. Sieve Series) range, it will often be
preferred to spray dry as much of the formulation as is
feasible, so as to obtain substantially uniformly shaped
globular particles. because the polyacetal carboxylate of
the present compositions can be adversely affected by heat
it may be desired to post-add it to other components of
the product that have previously been spray dried to form
what may be referred to as "base" beads. If the polyacetal
carboxylate is to be post-added it will be preferred that it
be of essentially the same shapes, particle sizes and
approximate density as the rest of the composition so as to
inhibit segregations during shipping and storage. However,
- 16 -
~L~3~561
even if more finely divided powdered polyacetal carboxylate
is employed, such as that of particle sizes in the lo or 160
to 200 or 325 mesh (or sieve number) range, it has been
found that such particles will often adhere to the larger
beads, maintain the product in the desired size range and be
essentially non-segregating (although, of course, results will
not be as good in this respect as when the various components
of the composition are all of the same sizes, shapes and bulk
density).
lo If the polyacetal carboxylate is spray dried with
the detergent composition care will be exercised to prevent
its decomposition due to its exposure to high spray tower
drying air temperatures. When spray drying is unavailable
or when costs are to be minimized the various components of
the present compositions may be mixed together, as powders,
and may be agglomerated to the desired lo to 100 sieve size,
or they may be mixed together as fine powders, usually in
the 100, 160 or 200 to 325 mesh range. When a non ionic
detergent is to be present in the product in a significant
proportion the major proportion thereof may be post-sprayed
onto previously spray dried beads or onto particles ox other
components of the composition. Normally, no more than about
4% of non ionic detergent, on a final product basis, will be
in a spray dried product, unless added after spray drying,
due to decomposition of the non ionic detergent that can occur
- 17 -
9561
at elevated tower temperatures when more than a relatively
small proportion thereof is present in the cxutcher slurry
being spray dried. Other temperature sensitive components
of the product may also be post-added so as to avoid undesir-
able subjections to elevated temperatures. Thus, if bleaching agent, such as sodium perorate, is to be present
it the for~ulation,it will ye post-added, as will be enzyme
powder, perfume and other heat sensitive components. On the
other hand, materials like the inorganic builders, such as
sodium carbonate, sodium bicarbonate, sodium silicate and
zealots, and fillers, such as sodium sulfate, help to make
strong, attractive and free flowing spray dried beads and
preferably will be incorporated in crutches slurries to be
spray dried for their physical characteristics, as well for
their building and filling functions.
In the practice of the washing process of this
invention, wherein soiled (and stained) fibrous materials,
such as conventional clothing and "laundry" fabrics, of
cotton, polyester-cotton blends, polyesters, acrylics,
nylons, acetates, rayons and various blends thereof, are
washed in an aqueous washing medium, such medium will contain
a suitable detergent, as described, and a polyacetal car boxy-
late of the desired calculated weight average molecular
weight. Preferably, such components will be parts of a
detergent composition but it is within the invention to
- 18 -
~23~3~;6~
charge such materials separately to the wash water. Although
improvements in wishing effects are obtainable with the
described compositions based on the previously mentioned
preferred non ionic detergent at intermediate or medium water
harnesses and at higher harnesses too, during both cold
water and hot water washing, the most significant improve-
mints in such cases are when the wash water is of medium
hardness. Also, when the detergent is the preferred anionic
detergent the most significant improvement is for cold water
washing with water of medium hardness, with cold water
washing with water of higher hardness also being improved
but not to as great an extent. Thus, preferred conditions
for washing with the invented compositions, whether anionic,
non ionic or mixed anionic and non ionic detergents are em-
plowed, will be in cold water (10 to 30C.) of medium hard-
news (50 to 150 ppm., as calcium carbonate). Such prefer-
fences also apply when the active components are employed and
are separately added to the wash water in an automatic
washing machine. Yet, in many cases the wash water may be
20 of a higher hardness, such as 150 or 200 to 300 or 400
ppm., and may be at a higher temperature, often up to 70C.
Preferably the washing will be done with a deter-
gent composition of this invention and from 0.05 to 0.5%
thereof will be used, more preferably 0.1 to 0.3~ and most
-- 19 --
1239~;61
preferably about 0.15%. Wash waters used will normally
contain from 0.0025 to 0.15% of the synthetic organic deter-
gent(s) and 0.0025 to 0.475% of the polyacetal carboxylate.
Preferred ranges of such materials will be 0.005 to 0.075~
and 0.01 to 0.15%, respectively and in the 0.15~ concentra-
lion of the composition preferred proportions of the deter-
gent and polyacetal carboxylate builder will be about 0.0225%
and about 0.0375~, respectively. The water employed will
desirably be of a hardness of 50 to 150 ppm. and at a
temperature in the range of 10 to 70C., preferably 10 to
30C., e.g., 21C. The water hardness will more preferably
be about 100 ppm., as calcium carbonate (usually with the
ratio of calcium to magnesium hardness being within the
range of 1:1 to 10:1, e.g., 3:2 to 4:1.
Under the conditions described, improved cleanings
are obtained using the preferred anionic and/or non ionic
detergents of this invention with the described low mole-
ular weight polyacetal carboxylate. When, in such compost-
lions, the low molecular weight polyacetal carboxylate is
replaced by a similar material but of higher molecular
weight (8034) the cleaning is significantly less, especially
in cold water washing in a medium hardness water. When
other detergents than those which have been taught herein to
be preferred are employed with the described polyacetal
carboxylate of this invention results obtained are notice-
ably inferior to those wherein the preferred detergents are
- 20 -
1~3g~6~
utilized with the polyacetal carboxylate. Also, with such
other detergents it has been noted that the higher molecular
weight polyacetal carboxylate appears to be slightly more
effective than the lower molecular weight carboxylate, which
is the opposite of the results noted with respect to the
invented compositions. Also, when the builder of this
invention is replaced by the prior art standard and preferred
builder, sodium tripolyphosphate, washing results are notice-
ably inferior to those of this invention.
The following examples illustrate but do not limit
the invention. Unless otherwise noted all parts are by
weight and all temperatures are in C., in these examples,
the rest of the specification and the claims.
EXAMPLE 1
15 Parts of Noodles, which is the sodium salt
of a polyethoxylated (3 ethoxies) higher fatty alcohol
(of an average of 12 to 15 carbon atoms) sulfuric acid,
obtainable from Shell Chemical Company, 30 parts of Builder
U (Lot 2547313, containing 83% of sodium polyacetal car boxy-
late of molecular weight of 5,250, 3.9% of sodium carbonate
and the balance mostly water) end 55 parts of sodium sulfate,
an hydrous, are dissolved at a concentration of 0.15~ in wash
water (0.0225~ of the detergent, 0.045% of the builder and
0.0825~ of the filler being in the water) at a temperature
of 21C. and of hardness of 100 ppm., as calcium carbonate
~23956~
(with the Cam ratio in the water being about 3:2),
and the wash water is used to wash test swatches of various
soils and stains on various substrate fabrics in a
Tergotomete~laboratory washing machine, employing a ten
minute wash cycle. The swatches are dried and their light
reflectance are measured and from such reflectance of any
remaining soils and stains on the different materials, soil
Rand stain) removal indices are computed. The higher the
index the whiter the test swatch after washing and the more
effective the washing operation. Such test is repeated with
a standard control detergent composition formula, in which
sodium tripolyphosphate is substituted for the sodium
polyacetal carboxylate. A very significant improvement
(plus 21) over the control is obtaiIIed. Lyon such test is
repeated except for the replacement of the anionic Nudely
25-3S with non ionic Nudely 25-7 (condensation product of
seven moles of ethylene oxide with one mole of higher fatty
alcohol averaging 12 to 15 carbon atoms, obtainable from
Shell Chemical Company), an even greater improvement (plus
2Q 23) is noted. inn sodium linear dodecylbenzene sulfonate
is employed as the anionic detergent in place of the Nudely
25-3S a decrease in washing effectiveness, compared to the
control, is noted. However, when sodium linear dodecylbenzene
sulfonate is only a minor proportion, e.g., 1/10, of the
anionic detergent present, with the other such detergent being
the Nudely 25-3S, significant improvement over the control in
the detergency will be obtained.
395~i1
In the previously described experiments when a
higher molecular weight polyacetal carboxylate, Builder U
Lot No. 2538422, of a molecular weight of issue employed
instead of the lower molecular weight material previously
described improvements over the control are still obtained
with both Nudely 25-3S and Nudely 25-7 "formulas". However,
the improvements are not as great and it is evident that the
washing processes utilizing the lower moo wt. polyacetal
carboxylate are significantly more effective than those in
which the higher mol. wt. carboxylate is present. Also, when
the previous experiment, in which sodium linear dodecylbenzene
sulfonate was employed, is repeated but the higher molecular
weight Builder U is employed, cleaning is inferior to the
control.
In the foregoing experiments, when instead of the
components being added separately to the wash water they are
first mixed together to form detergent compositions, either
by mixing of finely divided powders (particle sizes in the
20 range of 100 to 200 mesh) or by spray drying the anionic
detergent and filler from suitable aqueous crutches mixes to
particle sizes in the 10 to 100 mesh range, followed by
mixing with the polyacetal carboxylate of the same particle
size sand non ionic detergent, when used), or by agglomera-
lion of finely divided powders of components to particles in
the 10 to 100 sieve range, cleaning results by the described
tests are the same. Similarly, when the compositions are
- 23 -
12~C~61
made into liquid products, such as those wherein water is
substituted for the sodium sulfate filler, and when such are
employed at the same concentration in the wash water Tao%)
the same results are obtained.
Instead of employing "bare" formulas previously
given, aesthetically,functionally and commercially more
acceptable products may also be made in manners previously
described in the specification. Thus, a composition comprise
in 15~ of Nudely 25-7, 30% of Builder U (Lot 2547312), 10%
of sodium carbonate, 10~ of sodium silicate (Nash =
1:2.4), 1% of sodium carboxymethyl cellulose, 0.5% of perfume,
10% of moisture and the balance of sodium sulfate is made by
spray drying base beads of all the materials except the
non ionic detergent and Builder U, spraying melted non ionic
detergent onto the base beads and mixing with the product
the powdered Builder U, to produce particles in the 10 to
100 sieve size range. Such product will also show signify-
cant cleaning superiority against a control of the type
previously mentioned, and against similar products wherein
the higher molecular weight (8034) Builder U lot is employed
instead of the lower molecular weight (5250) material.
Similarly, when liquid compositions are made wherein some
of the water is replaced by 10% of ethanol, I of sodium
zillion sulfonate (hydrotrope) and 0.5% of perfume, leaving
41.5% of water (preferably deionized), all figures being on
- I -
~23~56~
a composition basis, the same results are obtainable.
EXAMPLE 2
When the experiments with Nudely 25 7 of Example 1
are repeated, with the only change being that the wash water
temperature is 49C., even greater improvement in washing
power compared to the control results. When the lower
molecular weight polyacetal carboxylate of this experiment
is replaced by the higher molecular weight material (Lot No.
2538422) it is found that the lower molecular weight polyp
acutely carboxylate washing process is significantly Beatrice shown by the fact that its SRI (soil land stain] removal
index) is significantly higher. Such is also the case when
compositions of the invention, whether in particulate,
solid, paste or liquid form, are made and tested in the same
manner.
EXAMPLE 3
When the experiments of Examples 1 and 2 are
repeated, utilizing water temperatures in the 10 to 30C.
range, e.g., 15 and 25C., and water harnesses in the 50
20 to 150 ppm. range, e.g., Andy 125 ppm., for the export-
mints of Example 1, and using temperatures in the 40 to
60C. range, e.g., 45 and 55C., and water harnesses in
the 50 to 150 ppm. range, e.g., 75 and 125 ppm., for the
experiments of Example 2, the same significant improvements
in washing power against the control will be obtained and
- 25 -
1~3~356~
the same improvements in washing effects when the lower
molecular weight polyacetal carboxylates are utilized
instead of the higher polymers will be noted.
EXAMPLE 4
A wash water containing 100 ppm. of hardness, as
calcium carbonate, and which is at a temperature of Casey
made containing 0.0113% of Nudely 25-7 and 0.0113% of
Nudely 25-3S, 0.045% of Builder U (mow.= 5250) and 0.0825%
of sodium sulfate. When various soiled fabrics are washed
in such wash water in the manner described in Example 1,
they are very satisfactorily cleaned and the Skis there-
of art hither than for a control composition in which the
Builder U is replaced by sodium tripolyphosphate. Also,
such indexes are higher than for similar wash waters in
which the Builder employed is of a molecular weight of
8034.
Similar results are obtainable when the Nudely 25-
7 is replaced by either Nudely 23-6.5 (condensation product
of one mole of higher fatty alcohol of 12 to 15 carbon atoms
and Ç.5 moles of ethylene oxide), Pluronics (condensation
products of ethylene oxide and propylene oxide), and condemn-
station products of nonyl phenol and polyoxyethylene ethanol,
and when 30% of the sodium sulfate is replaced by 10% of
sodium carbonate, 10% of sodium silicate and 10~ of moisture.
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~239~6~
EXAMPLE 5
When, in the experiments of the preceding examples
the proportions of components are varied ~10% and +25% and
when the concentrations in the wash water of such components
are varied +10% or ~25%, while still keeping within the
proportion ranges and percentages recited in the specification,
the detergent compositions and the wash waters so made will
have satisfactory washing properties, will be superior to
similar wash waters and compositions in which sodium Tripoli-
phosphate is employed instead of the lower molecular weightpolyacetal carboxylate, and will be superior to those combo-
sessions in which higher molecular weight polyacetal car boxy-
late is substituted for the lower molecular weight material.
Such is also the case when various other builders, including
sodium bicarbonate, Zealot PA, sodium sesquisilicate and
sodium citrate, are employed in a total building proportion,
and when adjutants, such as fluorescent brighteners, enzymes,
bleaches, clays, flow improving agents and fabric softeners,
are also present in functional proportions.
The invention has been described with respect to
various illustrations and examples thereof but is not to be
limited to these because it is evident that one of skill in
the art, with the present specification before him or her,
will be able to utilize substitutes and equivalents without
departing from the invention.
