Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~L~7Z~53
This invention relates to heavy duty laundry detergent
compositions. More particularly, it relates to such compositions
which include s~dium carboxymethyl-oxysuccinate (C~IOS), molecular
sieve zeolite, linear higher alkylbenzene sulfonate, sodium
silicate and anti-redeposition agent, which have better soil
removal properties than those of similar compositions which
contain pentasodium tripolyphosphate instead of CMOS. ~he
invented compositions preferably also include a higher fatty
alcohol polyethoxylate nonionic detergent and omit any phosphate
builder saLts and other phosphorus-containing compounds. Also
within the invention are methods of washing fabrics with the
invented compositions. -
In recent years much attention has been given to the
problem of formulating satisfactory heavy duty laundry detergents
without utili~ing phosphates. Because o~ claims that phosphorus
sometimes cause eutrophication of inland waters legislation has
been passed in various ~urisdictions limLting the contents
thereof in detergent compositions. Pentasodium tripolyphosphate
has been the most successful commercial builder salt for
synthetic anionic orga~ic detergent compositions and therefore
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replacement of it has been especially difficult. Among the
products that have been suggested for use as builders for heavy
duty laundry detergents are sodium carboxymethyl-oxysuccinate
(CMOS) and molecular sieve ~eolites, such as partially hydrated
type 4A molecular sieve zeolites. The latter compounds are
water-insoluble and act to sequester or tie up soluble calcium
ions in wash waters, thereby allowing the synthetic organic detergent
component of heavy duty laundry detergent compositions to wet
and emulsify lipophilic soils on the garments, articles and
fabrics to be cleaned, without interference from the calcium
present. Xowever, it has been noted that when laundry washed
with detergent compositions containing a sufficient proportion
o~ molecular sieve zeolite to be almost as effective as the
usual phosphate-containing detergents is line dried, rather
than dried in an automatic laundry dryer, a noticeable quantity
of the molecular sieve zeolite is retained in the articles
laundered, which is ob~ectionable.
CMOS is a soluble organic builder which i9 a good
8equestrant ~or calcium ion. However, as with various other
synthetic organic builders, it is comparatively expensive and
the use o~ a sufficient quantity thereo~ to produce essentially
the same extensive soil removal as the usually desirable :
proportion of pentasodium tripolyphosphate may so increase the
cost of the product as to make it commercially non-competitive.
Also, some handling characteristics, such as flowability,
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norl-tackiness and non-caking are effected adversely. IIowever,
in the present compositions, generally containing about equal
proportions of molecular sieve zeolite and CMOS, together with
usually lesser proportions Or linear higher alkylbenzene
sulfonate detergent, sodium silicate, as a supplementary
builder and anti-corrosion agent, and anti-redeposition agent,
a superior product is obtained, having better soil removing
properties than comparable formulations containing sodium
tripolyphosphate, molecular sieve zeolite or CMOS in place Or
the combination of molecular sieve zeolite and CMOS or contain-
ing a mixture of about equal parts of molecular sieve zeolite
and pentasodium tripolyphosphate. The invented formulation is
also significantly superior in cleaning power to zeolite~
citrate and zeolite-tartrate mixtures, with the same pr~portions
being employed, the essential substitution being that of the
citrate or t~trate for CMOS. Thus, a commercially competitive
heavy duty laundry detergent of better cleaning properties i5
made in accordance with this invention and i3 free M owing,
non-tacky and non-caking. The molecul~r sieve zeolite helps to
make up for the absence of pentasodium tripolyphosphate in both
calcium sequestering po~er and in promoting flowability and it
compensates for the presence of the CMOS in the formNla with
respect to flowability. Also, CMOS and silicate in the deter- :
gent prod~ct formulation help to sequester magnesium ions
while the molecular sieve zeolite acts most effectively against
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~72853
calcium ions. Of course such activities are important because both calcium
and magnesium ions are found in most hard waters.
In accordance with the present invention a heavy duty laundry
detergent comprises 15 to 20% by weight of a water insoluble molecular sieve
zeolite selected from the group consisting of A, X, Y, L, mordenite and
erionite and containing from about 1.5% to about 36% by weight of water, said
zeolite having a cation selected from the group consisting of sodium, potassium,
lithium, ammonium and hydrogen and having a mean particle diameter of about
0.5 to about 12 microns, 15 to 20% of a carboxymethyl-oxysuccinate selected
from the group consisting of water soluble alkali metal salts thereof and mix- -
tures of said salts containing some unneutralized carboxymethyl-oxysuccinic
acid; 5 to 25% of linear higher alkylbenzene sulfonate wherein the higher
alkyl is of 10 to 16 carbon atoms; 3 to 18% of sodium silicate wherein the
Na20:SiO2 ratio is in the range of 1:1 to 1:3.2; and 0.3 to 3% of an organic
anti-redeposition agent selected from the group consisting of carboxymethyl
cellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, lower
alkyl cellulose and hydroxy-lower alkyl lower alkyl cellulose. In preferred
aspects of the invention the molecular sieve zeolite is a hydrated or partial-
ly hydrated type 4A molecular sieve zeolite~ in which the sodium aluminosili-
cate is of SiO2:A1203 ratio of about 2 (on a molar basis, about one atom of
silicon per atom of aluminum), the carboxymethyl-oxysuccinate is sodium carboxy-
methyl-oxysuccinate, the linear higher alkylbenzene sulfonate is sodium tri-
decylbenzene sulfonate, the sodium silicate is of Na20:SiO2 ratio of about
1:2.4, the anti-redeposition agent is sodium carboxymethyl cellulose and also
contained is about 0.5 to 20% of higher fatty alcohol polyethoxylate having
6 to 15 ethoxy groups per mol and wherein the alcohol is of 12 to 18 carbon
atoms and about 0.5 to 2% of sodium higher fatty acid soap wherein the higher
fatty acid is of 12 to 18 carbon atoms.
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Also within the invention are methods of using the detergent
compositions in washing laundry and fabrics.
The molecular sieve zeolites utilized in making the
invented deter~ent compositions are water insoluble crystalline
alluminosilicate zeolites of natural or synthetic origin which
are characterized by having a network of uniformly sized pores
in the range of about 3 to 10 Angstroms, preferably about ~ A
(nominal), which size is uniquely determined by the unit structure
of the zeolite crystal. Of course, zeolites containing two or
more such networks of different size pores can also be employed.
The molecular sieve zeolite should also be a univalent
cation-exchanging zeolite, i.e., it should be an alumino-
silicate containing a univalent cation such as sodium,
potassium or lithium, when practicable, or of ammonium or hydroeen.
Preferably, the univalent cation associated with the zeolite
molecular sieve is an alkali metal cation, especially sodium or
potassium, most preferably sodium.
Crystalline types o~ zeolites utilizable as molecular
sieves in the invention, at least in part, include zeolites o~
the following crystal structure groups: A, X~ Y, L, mordenite
and erionite. Mixtures of such molecular sieve zeolites can also
be useful, especially when type A zeolite, e.g., type ~A, is
present. These preferred crystalline types of zeolites are
well known in the art and are more particularly described in
the text, Zeolite Molecular ~ieves, by Donald W. Breck,
~6~721~53
published in 1974 by John Wiley & 50ns. Typical commercially
available zeolites of the aforementioned structural types are
listed in ~able 9.6 at pages 747-749 of the Breck text.
Preferably the ~olecular sieve zeolite used in the
invention is a synthetic molecular sieve zeolite. It is also
preferable that it be o~ type A crystalline structure, more
particularly described at page 133 of the aPorementioned text.
Especially good results are generally obtained in accordance
with the invention when a type 4A molecular sieve zeolite is
employed, wherein the univalent cation of the zeolite is sodium ~-
and the pore size of the zeolite is about 4 Angstroms. The
especially pre~erred zeolite molecular sieves are described in
United States patent 2,882,243 which refers to them as Zeolite A.
Molecular sieve zeolites can be prepared in either a
dehydrated or calcined form, the latter ~orm containing ~rom
less than about 1.5% to about 3% of moisture, or in a hydrated
or water loaded ~orm, which contains additional water of
hydration and adsorbed water in sn amount up to about 30 to 36%
of the zeolite total weight, depending on the type of zeolite
employed. Normally a completea hydrated type 4A synthetic
zeolite will be o~ the ~ormula
( a20)6 (A1203)6 (SiO2)12 27 H20 or
Nal2(A102 Si2)12 27 H2
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when completely molecularly hydrated. ~owever, this product can
still adsorb or absorb additional moisture so that the upp~r
limit in moisture content is not about 22%,as calculated,
but may be higher. Preferably, hydrated or partially hydrated
~orms of the molecular sieve zeolite are employed in the practice
of this invention and these usually have a ~ater content of 18
to 28.5%, e.g., 20 to 22%. The manufacture of such crystals is
well known in the art. For example, in the preparation o~ 1
Zeolite A, referred to above, the partially hydrated or hydrated
zeolite crys-tals that are formed in the crystallization medium
(such as hydrous amorphous sodium aluminosilicate gel) are made
without the high temperature dehydration (calcining to 3% or ~ `
less water content) that is normally practiced in preparing such
crystals for use as catalysts, e.g., cracking catalysts. The
preferred form of zeolite in partially ~ydrated ~orm can be
recovered by filtering o~f the crystals from the crystallization
n~edlum and drying them in air at ambient temperature to ~luch an
extent that the water content thereof is as desired.
Usually the molecular sieve zeolite should be in
finely divided condition, such as crystals (amorp~ous or poorly
crystalline p~rticles may also ~ind some use) having mean
particle diameters in the range of about 0.5 to about 12 microns,
preferably 5 to 9 microns and especially about 5.9 to 8.3 microns9
e.g., 6.4 to 8.3 microns.
The CMOS constituent o~ the present detergent
compositions, carboxymethyl-oxysuccinate, normally employed as
1~7Z85.~
a water soluble salt, such as an aIkali metal salt, e.g.,
sodium carbox~methyl~oxysuccinate. ~he degreeofneutralization
oP this supplementary builder may vary and in some cases some
unneutralized carboxymethyl-oxysuccinic acid may be present.
However, normally the carboxyl groups will be converted to sPlt
form before formulation of the detergent ~roduct, during such
formulation or during washing with the composition. All the
carboxyls of the CMOC are preferably neutralized, as with a
sodium-containing base, to make them more effective as calcium
sequestrants but it is within this invention to utilize partially
neutralized CMOS, too. Thus, the mono- and di-salts and
mixtures averaging mono-, di- and intermediate salts (including
those intermediate di- and tri-) are also utilizable. While
C~IOC in its sodium salt form i9 highly preferred as the auxiliary
builder of this invention which cooperates with the zeolite and
silicate to give the present detergent products superior
properties, it is also contemplated that the CMOC may be
substituted in part, e.g., up to 50%, by other builders of
similar chemical structure. Thus, instead of the carboxymethyl-
oxy substitution on the succinic acid, carbox~ethyl-oxy,
carboxypropyl-oxy and carboxyisopropyl-oxy substitutions
may be utilized and instead of succinic acid, comparable acidic
compounds such as malonic acid, glutaric acia and adipic
acid, may be employed (with the different substitutents on
such acids, too) so long as they are operative. However, the
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~72853
use of CMOS is highly preferred and it will normally be
employed as a sodium salt, preferably the trisodium and/or
disodium salt.
The linear higher alkylbenzene sulfonate deter-
gent will usually b e of 10 to 16 carbon atoms, preferably
12 to 14 carbon atoms and most preferably about 13 carbon atoms
and will normally be neutralized with a suitable alkaline mate-
rial, of which the most preferred are such s~hich result in
alkali metal linear higher alkylbenzene sulfonates being produc-
ed, preferably the sodium salts of the linear higher alkyl-
benzene sulfonic acid. Other synthetic anionic organic deter- ;
gents may be present with the linear higher alkylbenzene sul-
fonates but normally will only constitute a minor proportion
of the total anionic detergent content of the present compositions.
Such supplementing anionic detergents may be of 8 to 26,
preferably 12 to 22 carbon atoms per molecule and usually will
include an alkyl or other aliphatic chain containing about 8
to 18 carbon atoms, preferably 10 to 16 carbon atoms and most
preerably will be straight chain alkyl. Such anionic detergents
include the alpha-olefin sulfonatesJ paraffin sulfonates, ethoxy-
lated alcohol sulfates, alkyl sulfates and sulfated higher alkyl
phenyl polyoxyethylene ethanols, all preferably as alkali metal
salts, such as the sodium salts. A list of such detergents
is found in United States patent 3,~37,339. The water soluble
higher fatty acid soaps, such as the sodium soaps of higher fatty
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~)728S3
acids of 12 to 18 carbon atoms may also be employed as anionic
detergents in the present compositions.
Nonionic detergent compounds are often utilized in the
present detergent compositions in mixture with a linear higher
alkylbenzene sulfonate de-tergent and with any other suitable
supplementing anionic detergent present. The nonionics will
normally be lo~er aIkylene oxide condensation products, such
as polyethylene oxides, which may sometimes have polypropylene
oxide present too but only to such an extent that the product is
still wat.er soluble. Preferred examples of such materials
are the higher fatty alcohol-polyethylene oxide condensates
wherein the higher fatty alcohol is of 10 to 18 carbon atoms,
preferably 12 to 15 carbon atoms and the ethylene oxide portion
thereof is a chain of 3 to 30 ethylene oxide units, preferably
6 to 15 ethylene oxide units and more preferably, about 10 to 13
ethylene oxide units. For example, a preferred nonionic
detergent of this type is Neodol*45-11, manu~actured by Shell
Chemical Comp~ny, wh~ch i6 a hi~her fatty alcohol polyethoxy-
ethanol containing about 11 ethylene o~ide groups per mole
(includin~ the ethoxy of the ethanol) ~nd having an average of
about 14 to 15 carbon atoms in the higher fatty alcohol. Other
primary alcohol condensation products include Plurafac*B-26 and
Alfonic*1618-65. ~ergitol*15-S-9, made by Union Carbide Corpora-
tion, exemplifies the suitable secondary alcohol condensation
products with ethylene oxide. Also useful are similar ethy].ene
oxide condensates of phenols, such as of nonyl phenol or isooctyl
phenol, knoun as Igepals*, made by GAF Corporation, but these are
not preferred.
In the present compositions there may also be em-
ployed any o~ a number o~ suitable amphoteric and cationic detergents
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~L~7Z85~
which are well known and, like the snionic and nonionic
detergents, builders, adjuvants and other intended components
of the present compositions, are described in the text
Surface Active Agents and Detergents, Vol. II, by Schwartz,
Perry and Berch, published in 1958 by Interscience Publishers,
Inc., especially at pages 25-138, and in Deter~ents and
Emulsifiers, 1969-1973 Annuals, by John W. McCutcheon.
The sodium silicate component of the invented
composition is one of Na20:SiO2 ratio in the range of 1:1
to 1:3.2, preferably 1:2 to 1:2.6 and most preferably about
1:2.4, e.g., 1:2.35. Such a compound is especially useful in -
the present compositions for its combination anti-corrosion
and building effects in con~unction with the zeolite molecular
sieve and CMOS. The silicate is espec~ally good as a builder
in wash waters containing magnesium ions and thereby usefully
complements the other builder materials under u5ual washing
conditions.
The w3e of an anti-redepositLon agent in the invented
compositions is especially important because o~ the presence
in the wash waters of insoluble, depositable particulate
ma~erial, including the molecular sieve zeolite. Of the
known anti-redeposition agents the most preferable to employ
is sodium carboxymethyl cellulose but also useful, either as
partial or complete substitutes for the sodium carboxymethyl ~ ;
cellulose (and only minor substitution is preferred) are ~
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polyvinyl alcohol, pol~vinyl acetate (which hydrolyzes to the
alcohol), polyvinyl pyrrolidone, lower alkyl celluloses,
e.g., methyl cellulose, ethyl cellulose, and hydroxy-lower
alkyl lower alkyl celluloses, e.g., hydroxypropyl methyl
cellulose, hydroxyethyl ethyl cellulose. In such latter
cellulose compounds the lower alkyl groups are usually of 1
to 3 carbon atoms.
In addition to the molecular sieve zeolites, CMOS
and silicate, other builder salts may also be present in the
invented compositions. Normally these are water soluble and
are alkali metal salts, preferably the sodium and potassium
salts o~ inorganic acids3 e.g., sodium carbonate, potassium
bicarbonate~ borax, pentasodium tripolyphosphate and tetra-
sodium pyrophosphate. However, the phosphates and borax are
often preferably omitted ~or ecologica]. reasons. Organic
builders may also be utilized in the present compositions,
such as trisodium nitrilotriacetate or NTA (which is still not
approved for general use in detergents~, sodium citrate,
potassium gluconate and hydroxyethyl iminodiacetate, disodium
salt. 0~ course, ~iller salts, such as sodium sul~ate and
sodium chloride, are normal constituents o~ detergent composi-
tions and may be employed. -
Various ad~uvants may be present for their special
activities, such as enzymes, e.g., proteolytic enzymes
(proteases) and amylotic enzymes (amylase); hydrotropes,
e.g., sodium toluene sulfonate; wetting agents; flow-improving
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agents, e.g., clays ~although the molecular sieve zeolite
usually performs such functions satisfactorily in the proportion
employed); bactericides, fungicides, fluorescent brighteners;
dyes; pigments; perfumes; emollients; stabilizers; fillers;
coating agents; and softeners. When bleachesJ e.g., sodium
perborate, sodium percarbonate, and activators for bleaching
are used they will usually be present in greater quantities than
other adjuvants.
The proportions of the various components of the
invented compositions should be held within the following
described ranges for good activities. The product should com-
prise ~and often may consist essentially of)preferably 15 to
20% of molecular sieve zeolite, more preferably about 17%;
tlle same ranges of percentages for CMOS; 5 to 25% of linear i`
higher alkylbenzene sulfonate, preerably 8 to 12% and more
preferably about 10%; 3 to 18% of sodium silicate, preferably
5 to 15% and more preferably about 8%; and 0.3 to 3%J pre-
ferably 0.3 to 1% and more preerably about 0.5~ of anti-
redeposition agent. The ratios of molecular sieve zeolite :
CMOS : linear higher alkylbenzene sulfonate ; sodium silicate : -
anti redeposition agent will usually be in the range of 1 : 0.5
to 2 : 0.2 to 1 : 0.3 to 2 : 0.02 to 0.2, preferably 1 : 0.7
to 1.2 : 0.4 to 0.8 : 0.3 to 0.7 : 0.02 to 0.1 and most pre-
ferably about 1 : 1 : 0.6 : 0.5 : 0.03. When nonionic
detergent is present in the formulation
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it will normally be ~rom 0.5 to 20% o~ the product, preferabl~ 0.5 to 2.5%
thereof and most preferably will ~e about 2~. When soap is present it will
usually be in a proportion from 0.3 to 3%, preferably 0.5 to 2% and most
preferably about 1%. Filler content will generally be in the range of 15
to 60%, preferably 25 to ~5% and most pre~erably about 35%. Moisture content
may be from 0.5 to 15%, usually being 2 to 10% and preferably 3 to 8%, e.g.,
7%, as "free moisture".
Any usual adjuvants present will normally total about 1 to 10%,
with individual ad~uvants generally being in the range of 0.01 to 5%. For
example, the content of fluorescent brighteners or optical dyes may be in
the range o~ 0.01 to 2%, normally being about 0.5 to 1.5%. The t ~ of
ad~uvants is preferably in the range of 1 to 5%, such as 2 to ~% and typical-
ly about 2.5% thereof may be present and will include perfumes, colorants,
flow promoting compounds and optionally, fungicides, bactericides and emol-
lients. I~ bleaches are present in these detergent compositions they will
normally be from 5 to 30%, including activators for bleaching percompounds,
and the~proportions of other components will ble reduced accordingly. Of
course, mlxtures of dif~erent types of individ~ual components within the in-
vention may be used, too.
~he various components of the detergent compositions m~y be blended
together by admixing powdered compounds but preferably crutcher mixes of
most of the components are spray dried, spray cooled, drum dried or otherwise
converted to globular "spray dried" form. Alternatively, various components
may be co-size-reduced to the desired particle size ranges. ~ormally, per-
fume, nonionic detergent, flow promoting agent and any heat-sensitive com-
porents will be post-added to tumbling spray dried detergent composition.
However, in some cases it may be desirable to promote ~low of tbe product by
post-adding a proportion of the molecular sieve zeolite, e.g., 10 to 25% of
the amount o~ molecular sieve ~eolite in the final product The globular
particles of detergent compositions may be classified or sieved so that over
90%, preferab.~y over 95% and most preferably, all tbereof passes through a
~o. 8 or No. 10 United States Standard Sieve Series sieve and less than 10%,
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pre~erably less than 5% and most preferably, 0% passes through a No. 100sieve. The rest of the product, which may be post-added, if in the solid
state, will normally be in powder form, with the molecular sieve zeolite
powder component being of the size previously mentioned, e.g., from 5 to 9
microns in diameter, and the other po~dered products being such that they
will pass through a ~o. 100 sieve and fail to pass a ~o. I~oo sieve, pref-
erably pasfing through a No. 1~0 sieve and resting on a No. 325 sieve. When
the nonionic detergent is in liquid form or may be readily liguefied, it may
be desirable to spray it onto the surfaces of the tumbling detergent globule-
powder mixture.
The washin~methods of this invention may be carried out at various
pH's and concentrations of the detergent composition in washing liquid medium
but normally the pH will be in the range of 8 to 12, preferably 8.5 to 10.5
ancl most preferably 9 to 10.5. The concentration of the detergent composi-
tion in the aqueous washing medium, which will usually be ordinary tap water,
will normally be from 0.05 to 2%, preferably being about 0.1 to 1%. Most
preferably, such concentration will be about 0.15% in the United States and
abo~lt o.8% in European countries wherein high concentrations of detergent
and low volumes of wash water have been employed in the conventional washin~
machines. Usually the laundry : wash water ratio will be from 0.03 to 0.2,
preferabl~ 0.04 to 0.1~ e.g., 0.05 or o.o6 for United States laundry practices
and about one to five times these ra-tios, e.g., about three times such
rat~os, for European practices. ~aterials washable with the invented com-
positions include cottons, polyesters, cotton-polyester blends, e.g., 55:45
blends, permanent press fabrics and all usual commercial fabrics.
~he present compositions are employed in the same manner as com-
parable commercial heavy duty laundry detergents. Thus, they may be used
for cold, warm and hot water washing, usually in the temperature range of
10 to 70 C. Excellent cold and warm water washings of ~arious types of
fabrics result, using ordinary automatic washing machines and normal washing
times, 3 to 45 minutes, preferably being from 5 to 20 minutes in the United
States and from 20 to 40 minutes according to European practices.
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1~72853
Various advantages of the invented compositions have already been
mentioned. The presence of the molecular sieve zeolite appears to help to
prevent staining o~ ~hite or light goods ~ith stains which might be removed
from colored goods or laundry containing colored soils. In such cases, in
the presence of the CMOS and other detergent composition constituents, the
molecular sieve zeolites appear to preferentially adsorb the color bodies ;
and thereby prevent them from being deposited on the white or lighter colored
goods, resulting in a lesser amount of discoloration thereof. Also, the
lowered content of molecular sieve zeolite results in less deposition thereof
on the clothing and the proportion of anti-redeposition agent present is
capable of maintaining most of the molecular sieve zeolite in suspension
in the wash water so that it does not become entrapped in the fabrics being
cleaned (which could occur during rinsing). The presence of the linear
alkylbenzene sulfonate detergent appears to assist in maintaining the sus-
pension of the molecular sieve zeolite, too. Of course, the combination of
various types of builders which are "sequestrants" for different types of
h~ dnesses favors ~etter wnshing by the anionic detergent (and accompanying
nonionic detergent, when employed). Thus, there are sienificant coactions
between the various components in the proportions in which they are employed
in the present detergent compositions.
~ he invention will be further illustrated by the following ex-
amples. Unless otherwise indicated all parts therein and in the specifica-
tion are by weight a~d all temperatures are in C.
EXA~PIE 1
A preferred detergent composition of this invention is made by
spray drying an aqueous crutcher mix of the components thereof and containing
about 60% of solids, in a countercurrent spray tower utilizing drying air at
about 250 C,, to a moisture content of about 6.5% and then spraying 0.5% of
perfume onto tumbling surfaces thereof. The perfumed spray dried detergent
composition includes, on a final product basis, about 10% of sodium linear
tridecyl benzene sulfonate, 17% of type I~A molecular sieve zeolite (the
SiO2:A1203 mol ratio of which is 2 and which contains 20% of moisture, is of ~`~
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pore sizes of about 4 ~ gstroms diameter and is of particle si~es in the
range of 5.9 to 803 microns in diameter), 17% of sodium CMOS (trisodium
salt), 0.5% of sodium carboxymethyl cellulose, 2% o~ ~eodol ~5-ll (higher :-
fatty alrohol polyethoxyethanol of about ll ethoxy groups per mol and in
which the higher fatty alcohol is of 14 to 15 carbon atoms per mol), 1% of
higher fatty acid soap ~herein the higher fatty acid i5 a mixture of hydro-
genated coconut oil ana hydrogenated tallow in 1:4 ratio, 35% of sodium
sulfate (as the anhydrous form), 8%of sodium silicate (Na20:SiO2 = 1:2.35)
and about 3% of various ad~uvants (fluorescent brighteners, perfume,
stabili2er, free oil [impurities in materials charged] and colorants). The
particle sizes of the spray dried beads are in the range of lO to 100 mesh,
United States Standard Sieve SPries. The CMOS, sulfate and CMC, as charged
to the crutcher, are powders of particle sizes such that they pass through a
No. 140 sleve and rest on a No. 325 sie~e, United States Standard Sieve
Series.
The detergent composition made i8 substantially homogeneous, free-
flowing and non-dusting, possibly in part due to the adsorption cf any excess
moisture in the spra~ dried product by the zeolite molecular sie~e. Also,
the product is substantially non-tacky and non-caking under ordinary storage
conditions.
In test washing of mixed laundr~ having an artificial test soil
deposited thereon, whlch laundry is composed of' test swatches of cotton,
cotton-polyester and permanent press treated cotton-polyester fabrics, the
detergent concentration in the wash water is 0.15%, the water employed has
150 parts per million of hardness (the clacium : magnesium hardness ratio,
calculated as calcium carbonate, being 3:2), the temperature is maintained
at 49C. and washing is continued for ten minutes in a laboratory Tergo-
tometer ~ washing machine. At the end of washing the wash water has a pH
of 9.2. The test f`abrics washed are rinsed and dried in the normal manner
and are read for whiteness (Rd on the Gardner Color Difference Meter). The
Rd for the pre~erred experimental composition described is 50Ø Thls indi-
cates that the cleaning power of the detergent composition is superîor to
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that of a similar composition, made the same way~ in which the combinationof the molecular sieve ~eolite and CMOS is replaced by an equal weight of
pentasodium tripolyphosphate ( Rd = 48.7); the molecular sieve zeolite
( Rd = 45.9); CMOS ( Rd = 48.5); equal parts of type 4A molecular sieve
zeolite and of pentasodium tripolyphosphate ( Rd = 46.8); equal parts of
the molecular sieve zeolite and of sodium citrate ( Rd = ~.5), and equal
parts of the molecular sieve Peolite and sodium tartrate ( Rd = 41.0).
In practical laundry tests the preferred composition is also
especially useful in removing various types of soils from the lalmdry. How-
ever, in such tests the water temperature ranges from 15 C. to 65C., thehardness thereof is from 50 to 250 parts per million of calcium carbonate
(mixed clacium and magnesium hardness), the washing times are from 5 to ~5
minutes, the machines employed are top loading and side loading, the deter-
gent composition : laundry weight ratio is from 0.01 to 0.1 and the laundry :
wash water ratio is from 0.03 to 0.2. No ob~ectionable deposits of molecular
sieve zeolite are found on laundry which is machine washed and subsequently
line dried and of course, no such deposits are found on such laundry which is
dried in an automatic clothes dryer.
The whitening power of the composition can be further improved by
replacing half of the quantity Or sodium sulfate present (17.5%) with penta-
sodiu~ tripolyphosphate, when such compound may be employed without violation
of l&w and without adverse effects on the ecology. Apparent brightness is
improvable when fluorescent brighteners are included in the formula as part
of the ad~uvant composition, especially when there is present a stilbene
fluorescent brightening compound, such as Tinopal ~ RB~ (Geigy), preferably
with Tinopal 5B~I Conc. in lesser proportion, the total proportion of the ;
fluorescent brighteners being about 1%. Stain removal and soil removal are
also improved by the addition to the composition of about 1% of Alcalase ~ ;
proteolytic enzyme. Further useful effects in removing stains and soils are
obtainable when a per compound such as sodium perborate tetrahydrate is
present, usually as a ma~or replacement for the sodium sulfate, e.g., con-
stituting about 20% of the detergent product. Such perco~pound is post-
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added to the spray dried product.
In variations of the above formula for the preferred invented
product the ~eodol and soap are omitted. In such cases the invented com-
positions are still better in washing effects than the various controls
described, from ~hich such components have also been removed. In other
variations of the formulation 20% of the linear aIkylbenzene sulfonate con-
tent is replaced by sodium higher fatty alcohol sulfate in one experiment,
30% of it is replaced by sodium paraffin sulfonate in another case and in
another instance 25% of it is replaced by alphaolefin sulfonate of essen-
tially the same chain length. In all such cases satisfactory detergents of
.
desirable characteristics, such as those described, are obtained. Such isalso the situation ~Then the proportion of sodium silicate present is in-
creased to 15% in the final product.
EXAMPLE 2
The compositions of Example l are made but with the substitution of
type ~A molecular sieve zeolite which i9 completely molecularly hydrated (22%
of water of crystallization, corresponding to 27 mols H20 per mol zeolite),
partially hydrated such molecular sieve zeolite containing about half as much
of water o~ hydration and an anhydrous type 4A molecular sieve zeolite. Use-
ful detergent products result in all such cases.
The compositions oP this example are ~urther varied by replacin~
the trisodium CMOS employed with disodium CMOS ~nd with monosodium CMOS and
by partially replacing it (20%) with carboxymethyl-oxysuccinic acid. UsePul
detergents of desirable cleaning power are also obtained. ~;
.. .
In a further variation of these formulas sodium silicates of
'. :'' ...
~a20:SiO2 ratios oP 1:2.0 and 1:2.6 are employed and good detergents sim-
ilarly result. ~his is also the case ~hen sodium carboxgmethyl cellulose is
replaced, to the extent of half the content thereof, with polyvinyl alcohol, ~ `
polyvin~l pyrrolidone~ hydroxypropylmethyl cellulose and methyl cellulose,
respectively. ~owever, it is considered that sodium CMC makes the best
detergents, those having the best soil anti-redeposition properties, and
therePore it is preferred to use it alone.
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EXAMPLE 3
Instead of the type 4A molecular sieve zeolite there are sub-
stituted the same quantities of types X and Y molecular sieve zeolites in
the formulas of Examples 1 and 2. The products resulting are useful deter-
gents by the tests described but for best detereency and physical properties
it is considered most desirable to utilize the type 4A molecular sieve
zeolite which is either hydrated or partially hydrated~ Anhydrous forms of
the various zeolites, unless they are hydrated during the manufacture of the
detergent composition, take additonal time durine the washing operation to
be hydrated first before they are able to effectively carry out their seques-
tering and building functions. Thus, they take longer to act and therefore
may be less effective in some instances.
EXAMPLE 4
The proportions of the various components of the compo~itions of
Examples 1-3 are varied within the ranges and ratios given in this specifica-
tion, normally beine chan~ed -30%, ~ 0% and -10%, within such ranges. ~he
products made are useful detergents, suitable for employment in various
cleaning operations. Of such detergents, those which contain no phosphorus
or are sub3tantially free of phosphorus (usually containing less than 1% of
phosphorus) are preferred, to comply with anti-eutrophication laws and reg-
ulations. --
EXAMPLE 5
~ he formulations of the previous examples are mndified by replacing
the nonionic detergent, when present, with a comparable nonionic detergent,
Plurafac B-26 ana alternatively~ with Alfonic 1618-65. In variations of the
manufacturing proceduse, the nonionic detergent is melted and sprayed onto
the surfaces of the tumbling spray dried components. GoGd detergents result. -i
~his iB also the csse when half of the sodium sulfate filler content is re-
placed by sodium chloride. In other variations of the manufacturing methods
the molecular sieve, C~OS and ~MC are post-added to spray dried besds of
the rest o~ the product components and the detergent composition resulting
is also superior to control compositions based on pentasodium tripolyphosphate
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107Z8S3
(wheretn the STPP is present in quantity equal to the sum of the CMOS and
molecular sieve zeolite). The detergent composition is also made by co-size-
reducing the various powders to the 10 to 100 mesh range (the zeolite adhering
to the larger sized particles). The products so made are also acceptable
detergents, comparable in performances to those previously described and
superior to the various controls mentioned.
!~ -
The invention has been described with respect to various illustra-
tions and embodiments thereof but is not to be limited to these because it is
evident that one of skill in the art will be able to use substitutes and
equivalents without departing from the spirit of the invention.
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