Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~i~S347
This invention relates to insoluble detergent builder
materials in particulate form which has been agglomerated or
otherwise formed into larger readily disintegrable particles with
the aid of a binder or equivalent continuous phase material. It
also relates to detergent compositions comprising such products
together with particles of similar sizes containing a synthetic
organic detergent and a water soluble carrier for the detergent,
such as a builder or filler.
Built synthetic organic detergents based on linear higher
alkyl benzene sulfonate synthetic organic detergent and pentasodium
tripolyphosphate have in the past been the accepted standards
for good detergent performance, the linear higher alkyl benzene
sulfonate being biodegradable and an exceptionally effective
detergent and the polyphosphate builder salt being a strong, yet
safe builder for the detergent. Xowever, because phosphates have
in recent years fallen into some disfavor due to their suspected
contribution to the eutrophication of inland lakes and rivers and
because of governmental legisIation and regulations enacted and
implemented as a result thereof, extensive experimentation has
recently been conducted with various other materials thought
possible to have building effects, among which are the carbonates,
silicates, borax, trisodium nitrilotriacetate (~TA) and host of ~.
,
.
:. . .
~534~
organic sequestrants, polyelectrolytes, chelants and other products
which it was thought might promote detergency of synthetic organic
detergents. Unfortunately, many of such proposed replacements for
phosphates, while not contributing as greatly to the eutrophication
of inland waters as the phosphates are alleged to do, have been
found to possess other detrimental properties. Some are poisonous,
some have been suspected of contributing to the development of
cancer, some are unstable on storage, some impart undesirable flow
and processing properties to the product, some are malodorous and
some react with other desired components of the built detergent
composition. Accordingly, complete agreement has not been reached
as to which of such products, if any, may be suitable phosphate
replacements.
Recently it has been discovered that zeolites, especially
certain synthetic amorphous zeolites and crystalline molecular
sieve zeolites, preferably in at least partially hydrated
condition, although water insoluble, are useful ion exchangers or
ion exchange agents for calcium ion and as a result of this
property, measurably improve the detergency of synthetic organic
detergents, especially those of the anionic type, and are also
useful with nonionic detergents. Although the water insoluble
~!
zeolites, especially the sodium aluminosilicates of such structure,
are useful builders and measurably improve detergency so that they
may be employed to partially replace phosphates and in some
instances completely replace them as builders in commercial heavy
duty detergent compositions, it has been found that because they
y~.
5~7
are insoluble materials there may be a tendency for them to
deactivate hardness ions more slowly than the polyphosphates,
especially if they are initially in anhydrous form, and sometimes
also to deposit objectionably on textiles washed with detergents
containing them. In spray drying heavy duty detergent compositions
it appears that the problem of-insoluble zeolite depositing on
washed laundry may sometimes be accentuated, apparently because in
the spray drying operation the molecular sieve zeolite is formed
into larger particles which do not as readily disperse (possibly
because of being cemented together by silicate) as a post-added
zeolite of ultimate particle size below 15 microns diameter does
and therefore may be caught in the fabric and held there, sometimes
whitening it, which may be objectionable when the treated fabric
is dark colored and is intended to remain so. Also, because the
zeolite particles are sometimes rather firmly held by the other
portions of the spray dried particle matrix they are slower to be
released into the wash water and therefore do not act as quickly
as possible to counteract hardness ions in the water. Better
building action is obtainable when zeolite particles of very fine
(micron and submicron) sizes are quickly released into the wash
~ater than is obtainable from spray dried beads containing such
zeolites, especially such beads containing silicates, too.
Although the possible deposition of molecular sieve zeolite
powder on colored laundry does not appear to be a problem when
the laundry is tumble dried after washing, in which tumbling
ll~S~34~
operation the flexings of the laundry and the turbulent flow of
the drying air tend to remove the molecular sieve zeolite powder
from the items washed, it still represents a problem when laundry --
is line dried, drip dried, damp dried or hanger dried, especially
after cold water washing.
Quick dispersiblity of the zeolite powder is possible -
by separate addition of it in finely divided form to the wash
water, preferably before the other detergent composition constituents. -~
Also, it may be post-added to the other components of the detergent
composition and mixed with such dry components so that separate
addition to the wash water is not required. Of course, separate
measurings and additions are tlresome and time consuming and do not
find favor with today's homemaker. Also, separate addition of the
zeolite powder to other dried detergent components can result in
sifting, stratification or other segregation of the detergent
components by particle size, with the molecular sieve zeolite
powder usually collecting at the bottom of the box of detergent
composition and thereby not being available for use in the
desired proportion when the product is first employed, thus leading
to negative evaluations of the product's performance as a
detergent. Furthermore, the finely divided zeolite powder, when
dispensed, may cause dusting problems due to its fine particle
size. Such problems have been overcome by the present invention
and a superior non-segregating, dust-free and effective detergent
composition results which is of an attractive uniform appearance,
does not have the detrimental characteristics of spray dried or
'k~`~ ,
11~5347
post-added molecular sieve zeolite-based detergents, as previously known,
and is readily manufactured by techniques conventionally employed in the
detergent industry. German Offenlegungsschrift P 2,535,792.0 teaches the
sorption of nonionic detergent on a crystalline sodium aluminosilicate but
the sorbent is higher in silica content than the present sorbent and is less
useful as a detergent builder. Netherlands patent application 75/10506
described agglomeration of zeolites with mixtures of hydrated salts.
In accordance with the present invention there is provided a readily
disintegrable insoluble detergen* builder particulate agglomerate comprising
a plurality of finely divided ion exchanging zeolite builder particles held
together by a binder, with the agglomerate particles being substantially
within the 4 to 180 mesh range. Preferably the readily disintegrable
insoluble detergent builder particulate agglomerate comprises a plurality of
finely divided synthetic zeolite builder particles of formula
(Na20)x- ~A123)y- (Si2) z WH2
wherein x is 1, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to
3.5, preferably 2 to 3 or about 2 and w is from O to 9, preferably 2.5 to 6,
held together by a water soluble binder, with the agglomerate particles being
substantially within the 4 to 180 mesh range or a part of said range which is
the same as or like that for a complementing portion of a detergent composition
which is spray dried.
In another aspect, the invention provides a particulate detergent ;~
composition comprising a mixture of (A) particulate, builder agglomerates
comprising from about 10% to 90% by weight of finely divided calcium ion
exchanging zeolite builder particles having the chemical formula
2 2 3 y 2 z 2
wherein M is a metal ion selected from the group consisting of sodium and
potassium, y is from 0.8 to 1.2, z is from 1.5 to 3.8 and w is from O to 9,
said particles having an ultimate particle diameter below 15 microns, and
about 90% to 10% by weight of a binder for said zeolite particles selected
from the group consisting of water-soluble starches, gums, sugars, synthetic
organic polymers and mixtures thereof, and (B) separate detergent particles
-- 5 --
B
. . . , ... ~ ,." ,. . . . ..
11~5~
containing 4% to 40% by weight of a water-soluble synthetic organic detergent,
10% to 60% by weight of a water-soluble builder salt and 10% to 80% by
weight of a water-soluble filler salt, the weight ratio of said builder
agglomerates to said separate detergent particles being in the range of ~1:10 to 5:1, with substantially all of the particles of said composition : `
being within the 4 to 180 mesh range (U.S. Standard Sieve Series). Also ~.
within the invention is a method for the manufacture of such -
- 5a -
B
,, , . .~ . ,,
, ~
agglomerate. While the use of water soluble binders is highly
preferred, it is also possible to use fusible binders, which
melt or otherwise break apart at the temperature of the wash water
but if employed such are usually used with a water soluble component
too.
The zeolites utilized in the present in~ention include
the crystalline, amorphous and mixed crystalline-amorphous zeolites
of natural or synthetic orlgin or mixtures thereoflthat can be of
satisfactorily quick and sufficiently effective hardness ion
counteracting activity. Pre~erably, such materials are able to
react sufficientl~ rapidly with a hardness cation such as one of
calcium, magnesium, iron and the like, to soften wash water before
adverse reactions of such hardness ions with the synthetic organic
detergent component of detergent compositions made according to the
present invention. A useful range of calcium lon exchange
capacities is from about 200 milligram equivalents of calcium
carbonate hardness per gram of aluminosilicate to 400 or more
; of such milligram equivalent~(on an anhy~rous ba~is). Preferably
such range is of about 250 to 350 milligram equivalents per gram.
; The water insoluble crystalline aluminosilicates used
are often characterized by having a network of substantially
~ .
?~
_6-
`' 11~i;~47
uniformly sized pores in the range of about 3 to 10 Angstroms,
often being about 4 A (nominal), such size being uniquely determined
by the unit structure o~ the zeolite crystal, Of course, zeolites
containing two or more such networks of different pore sizes can
also be satisfactorily employed, as can mixtures of such crystalline
materials with each other, and with amorphous materlals, etc.
The zeolite should be univalent cation-exchanging
zeolite, i,e., it should be an alumino~illcate of a univalent
cation such as sodium, potasslum, llthium (when practicable) or
~ liother alkall metal~ ammonium or hydrogen. Preferably the univalent
cation of the zeolite molecular sieve is an alkall metal cation,
especially sodium or potassium and most preferably, ls sodlum,
but various other types arelalso useful.
Crystalline types o~ zeolite utilizable as moIecular
1~ sieves ln the invention, at least ln part, include zeolltes of
the following crystal structure groups: A, X, Y, L, mordenite,
and erionite, of which ~ypes A and X are prePerred. Mixture~ of
such molecular sieve zeolltes can also be u8eful, especially
when type A zeolite is pre~en~. These crystalllne types of
zeolites are well known in the art and are more particularly
described in the text Zeollte Molecular Sieves by Donald W. Breck,
published in 1974 by John Wiley & Sons. Typical commercially
avallable zeolites of the aforementioned structural types are
listed in Table 9.6 at pages 747-749 of the Breck text, which
table is incorporated herein by reference.
-7-
Preferably the zeolite used in the invention is synthetlc
and it is also pre~erable that it be of type A or silllar structure,
particularly described at page 133 of the aforementioned text.
Good results have been obtained when a Type 4A molecular sieve
zeollte is employed, wherein the univalent cation o~ the zeolite
is sodium and the pore size of the zeolite i5 about 4 Angstroms.
Such æeolite molecular sieves are described in U.S. Patent
2,882,243, which refers to them as Zeolite A.
Molecular sieve zeolites can be prepared ln either a
dehydrated or calcined form which contains from about 0 or abouk
1.5~ to about 3~ of moisture of in a hydrated or water loaded
form which contains additional bould water in an amount from about
4 up to about 36~ of the zeollte total weight, depending on the
type of zeollte used. The water-containing hydrated-form of the
molecular sieve zeolite is preferred in the practive of this inven-
tion when such crystalline product i3 used. The manu~acture o~ such
crystals is well known in the art. For example, in the preparation
of Zeolite A, reffered to above, the hydrated zeollte crystals that
are formed in the crystallization medium (such as a hydrous
amorphous ~dium aluminosilicate gel) are used without the high
temperature dehydration (calcining to 3~ or less water content)
that is normally practived,in preparing ~uch crystals for use as
catalysts, e.g., cracking catalysts. The crystalline zeolite,
in either completely hydra,ted or partially hydrated form, can be
recovered by filtering off the crystals from the crystallization
S34~
medium and drying them in air at ambient temperature so that their
water contents are in the range of about 5 to 30% moisture, prefer-
ably 15 to 22%. However, because of the method of manufacture
of the present invention the moisture content of -the molecular
sieve zeolite being employed may be even as low as 0 percent
at the start of the manufacturing process because during the
blending with binder material (when water is also present) the
zeolite is converted to a more desirable, at least partially
hydrated state.
The zeolites used as molecular sieves should often also
be substantially free of adsorbed gases, such as carbon dioxide,
since such gas-containing zeolites can produce undesirable foaming
when the zeolite-containing detergent is contacted with water;
however, sometimes the foaming is tolerated and may be desirable.
Preferably the zeolite should be in a finely di~ided
state with the ultimate particle diameters being below 15 microns,
e.g., 0.005 to 15 microns, preferably being from 0.01 to 10
microns and e-specially preferably of 0.01 to 8 microns mean
particle size, e.g., 4 to 8 microns, if crystalline and 0.01 to
0.1 micron, e.g., 0.01 to 0.05 microns, if amorphous.
Although the crystalline synthetic zeolites are more
common and better known, amorphous zeolites may be employed instead
and are often superior to the crystalline materials in various
important properties, as will be described, as may be mixed
crystalline-amorphous materials and mixtures of the various types
.:
of zeolites described. The particle sizes and pore sizes of such materials
will usually be like those previously described but variations from the
described ranges may be made, providing that the materials function
satisfactorily as builders and do not objectionably overwhiten dyed
materials with which they are treated in aqueous media.
Various suitable crystalline molecular sieve zeolites are
described in Belgian Patent No. 828,753 and published German patent
specifications Nos. P 25 38 679.2, P 26 56 009.8 and P 26 56 251.6.
Various other such compounds are described in British patent specification
No. 1,429,143. Other useful such molecular sieve zeolites are illustrated
in British patent specifications Nos. 1,473,201, 1,473,571, 1,437,512
and 1,464,427.
The manufacturings of amorphous and mixed amorphous-crystalline
aluminosilicate ion exchange zeolites are described in British patent
specification No. 1,470,250. A preferred ion exchange zeolite is the
amorphous zeolite of Belgian patent 835,351 of the formula
- 10 -
' .
M20-A1203- (SiO2) wH20
wherein z is from 2.0 to 3.8 and w is from 2.5 to 6~ especially when
M is sodium. Such patent and applications are also incorporated
herein by reference to avoid the necessity for lengthy recitations
of such materials, methods for their manufacture and uses, etc.
The water soluble binders employed to agglomerate or
otherwise hold together the finely divided zeolite builder particles
are binding substances which satisfactorily hold such particles
together when they are dried or substantially dry, e.g., of free
moisture contents of less than 5%, (not counting water of hydration
or water held by the zeolite) but rapidly dissolve and release such
particles when the agglomerates are plunged into contact with an
aqueous medium, such as the wash water. Such effect is obtained over
usual storage condition temperature and use temperature ranges, such
~s -20 to 40C. and 10 to 80C., respectively. The binders, as
described herein, are water soluble crystalline
B
. .. .... . ...
-
11~;5347
or non-crystalline materials which meet the mentioned test, keeping the ag-
glomerated particles intact during normal handling, as when the product is
being filled and shipped, and yet permitting or promoting rapid dissolution
of the binder and dispersion of the finely divided molecular sieve zeolite
particles in sizes like their ultimate particle sizes when brought into con-
tact with water. The dissolution speed is such that the molecular sieve zeo-
lites have the described quick calcium - "neutralizing" action at the speed
previously mentioned. The rapidities of solution of the binder and disper-
sion of the zeolite particles may be increased by utilizing in the agglomer- -~
ate (or in the balance of the composition or part in each) an effervescing
material or mixture so that rupturing of any agglomerate particles will be
aided by the deYelopment of effervescence and dissolving and dispersion of
the particle components will thereby be even more rapidly achieved. Thus,
sodium carbonate or preferably sodium bicarbonate may be combined with -the
exchange zeolite binder mix and the balance of the detergent composition may
include citric acid, monosodium phosphate, boric acid or other suitable acid-
ifying material, preferably encapsulated or agglomerated with the bicarbon-
ate, for reaction with it to generate carbon dioxide.
;, The preferred binders are the water soluble starches, salts, gums,
sugars, polymers and nonionic surface active materials and mixtures of differ-
! ent types of such materials within a particular class and mixtures of typesfrom different classes, either two or more, may be employed. Of the binders
starches are preferred because of their very favorable combination of good
binding and fast dispersing properties. Starches usually occur as discrete
particles or granules having diameters in the 2 to 150 microns range and
while most of the starches contain from 22 to 26% of amylose and 74 to 70% of
amylopectin, some starches, such as waxy corn starches, may be entirely free
of amylose. It is intended to include within the term "starch" the various
types of natural starches, including corn starch, potato starch, tapioca, cas-
sava and other tuber starches, as well as amylose and amylopectin separately
- 12 -
, -
S3~7
or in mixtures. Furthermore, it is also intended that such term stand for
hydroxy-lower alkyl starches, hydroxyethyl starch, hydroxylated starches,
starch esters, e.g., starch glycolates, and other derivatives of starch hav-
ing essentially the same properties, e.g., partially hydrolyzed starches, and
similarly such derivatives of the major amylose and amylopectin components of
the starch are also included within the description. Related cellulosic com-
pounds and derivatives thereof are included herein within the class of gums,
and related carbohydrates, such as sugars (hydrolysis products) are also sep-
arately classified herein. Lower, as used above, means from 1 to ~ carbon
atoms.
Starches are particularly useful in the practice of the present in-
vention because they form thick aqueous solutions which have adhesive proper-
ties and therefore can be readily employed to agglomerate the molecular sieve
zeolite particles. Yet, such agglomerated particles, upon drying or sorption
of moisture from the starch solution by the zeolite, can be broken apart into
pieces of desired size (alternatively they can be controllably agglomerated
to such particle sizes) for use with similarly sized complementary detergent
composition particles. Although they are excellent agglomerating means and
can serve as a continuous phase which may include desira~le small size parti-
cles between zeolite sieve particles, when such agglomerated particles areplaced in water the starch swells, sufficiently weakening the bond to allow
it to be broken by the action of the agitated water and thereby rapidly dis-
persing the insoluble particles in the wash water. In addition to its de-
sirable adhesive and dissolving properties starch is very useful in the pres-
ent application because it is harmless in the product itself and when dis-
charged into sewers and ultimately, into inland water.
Gums and mucilages, included here within the meaning of gums, are
carbohydrate polymers of high molecular weight, obtainable from plants but
also able to be made synthetically. Most of them can be dispersed in cold
water to produce viscous mucilaginous solutions which do not gel but it is
11~5~;}47
intended to include within the meaning of the word gum herein those materials
which may be made synthetically and those which can also gel. Among some of
the plant gums that are of commercial importance may be mentioned arabic,
ghatti, karaya and tragacanth, among those normally classified as plant gums,
and guar, linseed, locust bean gums and mucilages. The seaweed mucilages or
gums such as agar, algin and carrageenin, are also included within this group,
as are the gum-like polysaccharides of the hemicellulose group of carbohyd-
rate polymers having a high pentosan content:
Among the synthetic gums the most favored are the carboxymethyl cel-
luloses such as sodium carboxymethyl cellulose, which also has a strong anti-
redeposition action in detergent compositions. Other synthetic gums which act
as anti-redeposition agents of this type include hydroxypropyl cellulose,
methyl and ethyl celluloses, hydroxymethylpropyl cellulose and hydroxyethyl
cellulose.
Sugars, such as sucrose and corn syrup are also useful water sol-
uble materials and for them there can be substituted various others of the
known pentoses and glucoses. ~he polymeric materials are those (except for
surface active polymeric materials) which are composed of a multiplicity of
the same (or different) monomeric groups and the term is intended to be em-
ployed as a residual class, excluding the starches, gums and sugars. Thus,various water soluble polymeric materials are included within this group,
such as the commercial preparations Polyclar ~ , (a polyvinylpyrrolidone,
made by GAF Corp.) Carbopol ~ (B.F. Goodrich Chemical Co.) and Carbowax ~
(Union Carbide Corp.). However, the most preferred of the synthetic polymers
is polyvinyl alcohol, alone or in mixture with polyvinyl acetate. Such prod- ;
uct is especially desirable because it too, like sodium carboxymethyl cellu-
lose (and PVP too~ to some extent), possesses excellent anti-redeposition
properties, helping to hold laundry soil dispersed in suspension without hav-
ing it redeposited on washed laundry. Also, polyacrylamide may be used in
partial or complete replacement of one or more of the other mentioned polymers.
- 14 -
`` 11t3'5~4~
Among the various salts that may be employed it is most desirable
to utilize those which have sufficient film strength to satisfactorily hold
together particular zeolite particles used. Among these are the various
phosphates, carbonates, sulfates, halides, bicarbonates, bisulfates, biphos-
phates, triphosphates, polyphosphates, pyrophosphates and borates, especially
such salts of inorganic salt-forming metallic ions, e.g., the aikali metal
salts. In place of the alkali metal salts, of which sodium is preferred, var-
ious other salt-forming ions may also be utilized, such as the triethanolam-
ine salts, diethanola~monium salts and ammonium salts. Most preferred of the
mentioned salts are pentasodium tripolyphosphate, tetrasodillm pyrophosphate,
tetrapotassium pyrophosphate, sodium carbonate, sodium bicarbonate, sodium
sulfate, potassium sulfate, a~monium sulfate, sodium chloride, potassium
chloride, borax, and sodium bisulfate. ~ormally the salts will be present in
at least partially hydrated form, with the crystals being formed serving to
join together the component zeolite particles, but anhydrous or partially hy-
drated salts may be utilized and the hydration or partial hydration thereof
may be effected in situ. The various builder and filler salts normally em-
ployed in detergent compositions are desirably utilized to hold the zeolite
particles together because they also perform useful functions in the final
detergent composition with which the aggregates are preferably ultimately in-
corporated.
The nonionic surface active materials are described at length in
McCutche~n's Detergents and Emulsifiers, 1973 Annual and in Surface Active
Agents, ~Tol. II, by Schwartz, Perry and Berch (Interscience Publishers,
1958), the descriptions of which are herein incorporated by reference. Such
nonionic surface active agents, preferably nonionic detergents, are usually
pasty or waxy solids at room temperature (20 C.) which are either sufficient-
ly water soluble to dissolve promptly in water or will quickly melt at the
temperature of the wash water, as when that temperature is above Lo c. The
nonionic surface active agents employed will not usually be those which are
- 15 -
. ... .
1~5~47
very fluid at room temperature because such might tend to make a tacky ag~
glomerate which would be poorly flowing and might lump or set on storage.
Typical useful nonionic detergents are the poly-(lower alkenoxy) derivatives r
that are usually prepared by the condensation of lower (2 to 4 carbon atoms)
alkylene oxide, e.g., ethylene oxide, propylene oxide (with enough ethylene
oxide to make a water soluble product), with a compound having a hydrophobic
hydrocarbon chain and containing one or more active hydrogen atoms, such as
higher alkyl phenols, higher fatty acids, higher fatty mercaptans, higher
fatty amines and higher fatty polyols and alcohols, e.g., fatty alcohols hav-
ing 8 to 20 or 10 or 12 to 18 carbon atoms in an alkyl chain and alkoxylated
with an average of about 3 to 30, preferably 6 to 20 lower alkylene oxide
units. Preferred nonionic surfactants are those represented by the formula
RO(C2H40)nH, wherein R is the residue of a linear saturated primary alcohol
(an alkyl) of 12 to 18 carbon atoms and n is an integer from 6 to 20. Typ-
ical commercial nonionic surface active agents suitable for use in the inven-
tion include Neodol ~ 45-11, which is an ethoxylation product (having an
average of about 11 ethylene oxide units) of a 14 to 15 carbon atom (average)
chain fatty alcohol (made by Shell Chemical Company); Neodol 25-7, a 12 to 15
carbon atom chain fatty alcohol ethoxylated with an average of 7 ethylene ox-
ide units; and Alfonic ~ 1618-65, which iB a 16 to 18 carbon alkanol ethoxyl-
ated with an average of 10 to 11 ethylene oxide units (Continental Oil
Company). Also useful are the Igepa ~ of GAF Co., Inc. In the above de-
scription higher, as applied to higher alkyl, higher fatty, etc., means from 8
to 20, preferably from 12 to 18. Also, supplementing or replacement propor-
tions of amphoteric or anionic surface active agents may be used with or in
replacement of some of the nonionic or sometimes, of all of it.
In place of the individual binders mixtures of two or more thereof
may be utilized. In some cases these will be highly desirable, as when the
mixture is that of a supplementing detergent (nonionic surface active agent),
anti-redeposition agent (starch or sodium carboxymethyl cellulose) and
- 16 -
. -. :
11(~5347
supplementing builder salts (STPP or Na2C03) or any two thereof. In such
cases the presence of such materials with the insoluble molecular sieve zeo-
lite, rather than bound with various other detergent composition constitu-
ents, promotes quick solution of the materials (and the nonionic surface
active agent further speeds this process) to have the wetting effect of the
nonionic surface active agent, the additional calcium sequestering effect of
any builder salt and the anti-redeposition effect of the sodium carboxymethyl
cellulose or equivalent gum obtainable before dissolution of a major propor-
tion of the detergent composition, the com-plementary portion, that containing
the synthetic organic detergent and soluble builder or filler salt. Of
course, some sodium carboxymethyl cellulose or starch may be included in the
complementary portion of the composition, as may be a proportion of zeolite
builder, supplementary builder, nonionic surface actlve agent and various
other materials, as may be desired, to balance the properties of the product.
Also, to balance such properties some ingredients of the normal complementary
part may be included with the zeolite agglomerate, too.
The water soluble synthetic organic detergent employed in the pres-
ent detergent compositions may include anionic, nonionic, cationic and ampho-
teric detergents but cationics will usually be omitted. Ampholytic and
amphoteric detergents are normally not as effective as anionic and nonionic
detergents and accordingly, the anionics, nonionics and mixtures of anionics
with nonionics are best in the separately spray dried complementing portions
of the detergent composition of this invention. Descriptions of various
materials of the mentioned detergent classes are found in McCutcheon's
Detergents and Emulsifiers, 1973 Annual and in Surface Active Agents, prev-
iously mentioned.
Suitable anionic water soluble surfactants include higher (8 to 20
or 12 to 18 carbon atom)alkyl benzene sulfonate salts, preferably higher
alkyl benzene sulfonates wherein the alkyl group contains 10 to 16 carbon
atoms. The alkyl group is preferably linear and especially preferred are
- 17 -
113~S~47
those of average alkyl chain lengths of about 11 to 13 or 14 carbon atoms.
Preferably also, the alkyl benzene sulfonate has a high content of
3- (or higher) phenyl isomers and a correspondingly low content (well below
50%) of 2- (or lower) phenyl isomers; in other terminology, the benzene ring
is preferably attached in large part at the 3 or higher (e.g., 4, 5, 6 or 7)
position of the alkyl group and the content of isomers in which the benzene
ring is attached at the 2 or 1 position is correspondingly low. One suitable
type of such detergent is described in United States patent 3,320,174. How-
ever, terminally alkylated LAS detergents are also used.
Also typical of the useful anionic detergents are the olefin sulfon-
ate salts. Generally they contain long chain alkenyl sulfonates or long chain
hydroxyalkane sulfonates (with the OH being on a carbon atom which is not di-
rectly attached to the carbon atom bearing the -S03 group). More usually,
the olefin sulfonate detergent comprises a mixture of these two types of com-
pounds in varying amounts, often together with long chain disulfonates or
sulfate-sulfonates. Such olefin sulfonates are described in many patents,
such as United States patents 2,061,618; 3,409,637; 3,332,880; 3,420,875;
3,428,654; 3,506,580; and British patent 1,139,158, and in the article by
Baumann et al. in Fette-Seifen-Anstrichmittel, Vol. 72, No. 4, at pages 247-
253 (1970). All the above-mentioned disclosures are incorporated herein by
reference. As indicated in these patents and the published literature, the
olefin sulfonates may be made from straight chain alpha-olefins, internal
ole~ins, olefins in which the unsaturation is in a vinylidene side chain
(e.g., dimers of alpha-olefin), etc., or more usually, mixtures of such com-
pounds, with the alpha-olefin usually being the major constituent. The sul-
fonation is usually carried out with sulfur trioxide under low partial pres-
sure, e.g., S03 highly diluted with inert gas such as air or nitrogen or
under vacuum. This reaction generally yields an alkenyl sulfonic acid, often
together with a sultone. The resulting acidic material is generally then
made alkal~ne and treated to open the sultone ring to form hydroxyalkane
- 18 -
., ~
11~5~7
` , .
sulfonate and alkenyl sulfonate. The number of carbon atoms in the olefin
is usually within the range of 10 to 25, more commonly 12 to 20, e.g., a mix-
ture of principally C12, C14 and C16, having an average of about 14 carbon
atoms or a mixture of principally C14, C16 and C18, having an average of about
16 carbon atoms.
Another class of water soluble synthetic organic anionic detergents
includes the higher (10 to 20 carbon atoms) paraffin sulfonates. These may
be the primary paraffin sulfonates made by reacting long chain alpha-olefins
and bisulfite, e.g., sodium bisulfite, or paraffin sulfonates having the sul-
fonate groups distributed along the paraffin chain, such as the products madeby reacting a long chain paraffin with sulfur dioxide and oxygen under ultra-
violet light, followed by neutralization with NaOH or other suitable base (as
in United States patents 2,503,280; 2,507,088; 3,260,741; 3,372,188; and
German Patent 735,096). The hydrocarbon substituent of the paraffin sulfonate ~ -
preferably contains 13 to 17 carbon atoms and the paraffin sulfonate will nor-
mally be a monosulfonate but, if desired, may be a di-, tri- or higher sulfon-
.~, : .,
ate. Typically, a paraffin disulfonate may be employed in admixture with the
corresponding monosulfonate, for example, as a mixture of mono- and di-sulfon-
ates containing up to about 30% of the disulfonate.
The hydrocarbon substituent of the paraffin sulfonate will usually
be linear but branched chain paraffin sulfonates can also be employed. The
paraffin sulfonate used may be terminally sulfonated or the sulfonate substit-
uent may be joined to the 2-carbon or other carbon atom of the chain. Sim-
ilarly, any di- or higher sulfonate employed may have the sulfonate groups
distributed over different carbons of the hydrocarbon chain.
- Other anionic detergents that can be used are the water soluble
:
salts or soaps of, for example, such higher fatty carboxylic acids as lauric,
myristic, stearic, oleic, elaidic, isostearic, palmitic, undecylenic, tri-
decylenic, pentadecylenic, 2-lower alkyl higher alkanoic (such as 2-methyl
tridecanoic, 2-methyl pentadecanoic or 2-methyl heptadeconoic) or other
-- 19 --
~.
11~5347
saturated or unsaturated fatty acids of 10 to 20 carbon atoms, preferably of
12 to 18 carbon atoms. Soaps of dicarboxylic acids may also be used, such as
the soaps of dimerized linoleic acid. Soaps of such other higher molecular
weight acids as resin or tall oil acids, e.g., abietic acid, may be employed.
One specific suitable soap is the soap of a mixture of tallow fatty acids and
coconut oil fatty acids (e.g., in 85:15 ratio). For the purpose of this
specification the soaps will be considered in the class of synthetic deter~
gents.
Other anionic detergents are sulfates of higher alcohols, such as
sodium lauryl sulfate, sodium tallow alcohol sulfate, sulfated oils, or sul-
fates of mono- and diglycerides of higher fatty acids, e.g., stearic mono-
glyceride monosulfate; higher alkyl poly (lower alkenoxy) ether sulfates,
i.e., the sulfates of the condensation products of a lower (2 to 4 carbon
atoms) alkylene oxide, e.g., ethylene oxide, and a higher aliphatic alcohol,
e.g., lauryl alcohol, wherein the molar proportion of alkylene oxide to alco-
hol is from 1:1 to 5:1 or 30:1; lauryl or other higher alkyl glyceryl ether
; suIfonates; and aromatic poly-(lower alkenoxy) ether sulfates such as the
sulfates of the condensation products of ethylene oxide and nonyl phenol
i (usually having 1 to 20 oxyethylene groups per molecule and preferably, 2 to
12). The ether sulfate may also be one having a lower alkoxy (of 1 to 4 car-
bon atoms, e.g., methoxy), substituent on a carbon close to that carrying the
sulfate group, such as a monomethyl ether monosulfate of a long chain vicinal
glycol, e.g., a mixture of vicinal alkane diols of 16 or 17 to 18 or 20 car-
bon atoms in a straight chain.
Additional water soluble anionic surfactants include the higher
acyl sarcosinates, e.g., sodium lauroyl sarcosinate; the acyl esters, e.g.,
oleic acid esters, of isethionates; and acyl N-methyl taurides, e.g., potas-
sium ~-methyl lauroyl- or oleyoyl taurides. Another type of anionic surfac-
tant is a higher alkyl phenol sulfonate, for example, a higher alkyl phenol
disulfonate, such as one having an alkyl group of 12 to 25 carbon atoms,
:
- 20 -
. .
`' ll~S3~7
preferably a linear alkyl of about 16 to 22 carbon atoms, which may be made
by sulfonating the corresponding alkyl phenol to a product containing in ex-
cess of 1.6, preferably above 1.8, e.g., 1.8 to 1.9 or 1.95 SO3H groups per
alkyl phenol molecule. The disulfonate may be one whose phenolic hydroxyl
group is blocked, as by etherification or esterification; thus the H of the
phenolic OH may be replaced by an alkyl, e.g., ethyl or hydroxyalkoxyalkyl,
e.g., a -(CH2CH2O) H group in which x is 1 or more, such as 3, 6 or lO, and
the resulting alcoholic OH may be esterified to form, say, a sulfate, e.g., ;~
-OS031~a. -~.
While the aforementioned structural types of organic carboxylates,
sulfates and sulfonates are generally preferred, the corresponding organic
phosphates and phosphonates are also useful as anionic detergents.
Generally, the anionic detergents are salts of alkali metals, such -
as potassium and especially sodium, although salts of ammonium cations and
substituted ammonium cations derived from lower (2 to 4 carbon atoms) alkan-
olamines, e.g., triethanolamine, tripropanolamine, diethanol monopropanol-
amine, and from lower (1 to 4 carbon atoms) alkylamines, e.g., methylamine,
ethylamine, sec-butylamine, dimethylamine, tripropylamine and tri-isopropyl-
amine, may also be utilized.
Of the anionic detereents the alkali metal salts of sulfated and
sulfonated oleophilic moieties are preferred over the carboxylic, phosphoric
and phosphonic compounds.
The nonionic detergent or surface active agent utilized with the
complementary material and often present in relatively minor quantity in the
crutcher mix when such is spray dried is of the type previously described as
a suitable binder.
Amphoteric organic surfactants are generally higher fatty carboxyl-
ates, phosphates, sulfates or sulfonates which contain a cation substituent
such as an amino group which may be quaternized, for example, with lower alk
groups, or may have the chain thereof extended at the amino group by conden-
- 21 -
:~lC~347
sation with a lower alkylene oxide, e.g., ethylene oxide. In some instances
the amino group may be a member of a heterocyclic ring. Representative com-
merical water soluble amphoteric organic detergents include Deriphat ~ 151,
which is sodium N-coco beta-aminopropionate (General Mills, Inc.), and
Miranol ~ C2M (anhydrous acid), which is the anhydrous form of the hetero-
cyclic diaminodicarboxylic compound of the formula
C H I ~ / CH2CH20CH2COOH
11 23 1 CH2COOH
(Miranol Chemical Co., Inc.).
Cationic organic surfactants include quaternary amines having a
water soluble anion such as acetate, sulfate or chloride. Suitable quater-
nary = onium salts may be derived from a higher fatty primary amine by con-
densation with a lower alkylene oxide similar to that described above for
preparation of nonionic surfactants. Typical cationic surfactants of this
type include Ethoduomeens ~ T/12 and T/13, which are ethylene oxide conden-
sates of N-tallow trimethylene diamine (Armour Industrial Chemical Co.) and
Ethoquad ~ 18/12, 18/25 and 0/12 which are polyethoxylated quaternary ammon-
ium chlorides (Armour Industrial Chemical Co.). Cationic surfactants also
include quaternary ammonium salts derived from heterocyclic aromatic amines
such as Emcol ~ E-607 which is N-(lauryl col~mino formyl methyl) pyridinium
chloride (Witco Chemical Corp.). Also sometimes classified as cationic sur-
factants are higher fatty amine oxides such as Aromox ~ 18/12 which is
bis(2-h~droxyethyl) octadecylamine oxide (Armour Industrial Chemical Co.) but
such are better considered to be nonionic.
The carrier for the synthetic organic detergent, preferably for one
of the anionic type, will usually be a builder or filler. Representative of
- 22 -
ll~S347
the inorganic builders which may be incorporated with the detergent are the
water soluble silicates, e.g., alkali metal silicates wherein the molar ratio
of metal oxide:SiO2 is about 1:1 or 1:1.5 to 1:3.2, preferably 1:2.0 to
1:2.5, e.g., of Na20:SiO2 ratio of 1:2.4, alkali metal polyphosphate salts,
such as pentasodium tripolyphosphate and tetrasodium pyrophosphate, borates,
such as borax and alkali metal carbonates, such as sodium carbonate and so-
dium bicarbonate. ~ormally hydrates of the salts are present in the product
but anhydrides may also be used. When phosphates are to be omitted from the
formula usually silicates or carbonates alone or in mixture are desirably em-
ployed as the inorganic builder salts. In addition to the inorganic buildersorganic builder salts may be utilized, such as alkali metal salts of nitrilo-
triacetic acid, citric acid, 2-hydroxyethyleneiminodicarboxylic acid, boro-
glucoheptanoic acid, polycarboxylic acids, e.g., polymaleates of lower molec-
ular weight (generally below 1,000, e.g., 400, 600 or 800), and polyphosphonic
acids, preferably all as their sodium salts. Also useful as carriers are
alkali metal sulfates, bisulfates and chlorides, usually of sodium, as fil-
lers and organic fillers or solubilizers, too, e.g., urea.
With the detergen-t composition, in addition to the main agglomerate
components, the molecular sieve zeolite and the binder, and the complementing
separate spray dried particles which include synthetic organic detergent and
filler and/or builder, various other adjuvants may be present, usually pref-
erably incorporated in the spray dried portion of the product except for
those which may be heat sensitive or are for improving flow properties.
Among such adjuvants are conventional functional and aesthetic adjuvants such
as bleaches, e.g., sodium perborate, colorants, e.g., pigments, dyes and op-
tical brighteners; foam stabilizers, e.g., alkanolamides, such as lauric my-
ristic diethanolamides; enzymes, e.g., proteases; skin protec~ting and condi-
tioning agents, such as water soluble proteins of low molecular weight, ob-
tained by hydrolysis of proteinaceous materials such as animal hair, hides,
gelatin, collagen (such materials may also be employed as binders); foam
- 23 -
S347
destroyers, e.g., silicones; fabric softeners, e.g., ethoxylated lanolin;
bactericides, e.g., hexachlorophene; opacifying agents, e.g., polystyrene
suspensions, behenic acid; buffering agents, e.g., alkali metal borates, ace-
tates, bisulfates; perfumes; and flow improving agents, e.g., ground clays.
The proportions of finely divided ion exchanging zeolite builder
particles and water soluble binder in the agglomerate particles will usually
be from 10 to 90% of the zeolite and 10 to 90% of the binder, preferably 20
to 80% and more preferably 30 to 70%. Most preferably, there will be no
other component except possibly minor adjuvants such as perfumes and flow
promoting materials and the total thereof will be no more than 5% of the ag-
glomerate particles. However, in some cases as much as 10 or 20% of adju-
vants may be present, especially in those cases wherein the product is to be
a component of a bleaching detergent composition or is to be used with such
a composition and the bleaching material is sensitive to heat, so that it
cannot be efficiently spray dried with the separate particles. In fact, as
much as 50% or 80 of perborate, percarbonate or peroxymonosulfate bleaching
agent may be present. In the absence of any such adjuvants the total of the
two components of the agglomerate particles is 100%, exclusive of any free
moisture present. The weights of components of the agglomerate particles
mentioned above are taken as is, including water o~ hydration of the zeolite
and water tied up with zeolite or binder. However, to prevent the product
from being tacky, sticky and poorly flowing the amount of free moisture is
desirably limited to 10%, is preferably less than 5% and in many cases will
be no more than 3%.
The spray dried separate particles of the product will normally
contain synthetic organic detergent, preferably of the anionic type, e.g.,
LAS, builder and/or filler and any other adjuvants that may be present.
Usually the heat stable adjuvants will be incorporated in the spray dried par-~
ticles so as to make them into unitary mobile particles of satisfactory flow
properties and appearance. Although spray drying is highly preferred, the
- 24 -
,, , , ,,, . , ~ : .
ll~S3~
separate particles may also be made by other methods, including spray cool-
ing, drum drying, tray drying, air drying and drying by hydration of anhyd-
rous components of a fluid mix. In utilizing these various methods oversize
particles or lumps may be size reduced to the desired size range and under-
size particles may be reworked. Normally the proportions of components in
the separate beads will be from 5 to 40% of the synthetic orgarlic detergent,
preferably 10 to 25% thereof, lO to 60% of builder salt, preferably 15 to 40%
thereof and 10 to 80% of filler salt, preferably 20 to 60% thereof, often
with from 1 or 2 to 10 or 20% of adjuvants, most or all of which will be lim-
ited to 5% and preferably to 2% of the separate beads.
The proportion of agglomerate particles to separate particles may
be varied as desired to produce the most acceptable detergent composition but
usually such proportion will be in the range of 1:10 to 5:1, preferably 1:10
to 4:1 and more preferably 1:5 to 3:1. The compositions of the detergents
made are considered to be better described by a total formula for them, as
they are obtained by mixing together the agglomerate and separate particles. ~`~
In such a composition the desired content of synthetic organic detergent will
usually be from 5 to 35%, preferably 5 to 25% and more preferably 10 to 25%,
with the content of builder salt (excluding the zeolite) being from lO to 60%,
preferably 15 to 40%, the content of' filler salt being about 10 or 15 to 60%,
preferably 20 to 40%, that of ion exchanging zeolite being about 5 to 50%,
preferably 5 to 40% and more preferably about 10 to 30% and that of binder,
which may also function as anti-redeposition agent, being about 0.5 to 20%,
preferably 1 to 15% and more preferably about 5 to 10%. Thus, preferred non
phosphate compositions may comprise from 5 to 25% of higher linear alkylben-
zene sulfonate wherein the higher alkyl is of 12 to 18 carbon atoms, about 5
to 20% of sodium silicate of ~a20:SiO2 ratio in the range of 1:1 to 1:3.2,
about 15 to 60% of sodium sulfate, about 5 to 40% of ion exchanging zeolite
and about 0.5 to 20% of starch or nonionic detergent binder, with such per-
centages being 8 to 15, 5 to 15, 20 to 50, 10 to 30 and 2 to 10%, respective-
- 25 -
æ
1~5347
ly for preferred formulations, in which formulations the LAS is sodium linear
alkyl benzene sulfonate wherein the alkyl is of 12 to 15 carbon atoms. Such
formulas may be varied by having some or all of the sodium silicate replaced
by sodium carbonate when it is the objective to make a non-phosphate deter-
gent or by pentasodium tripolyphosphate or other suitable polyphosphate when
the presence of phosphate builders is allowable. Also, an additional propor-
tion of 5 to 40% of such phosphate, preferably 10 to 25% thereof, may be
added to the other components (of the non-phosphate formulas) for the manu-
facture of phosphate detergents, in which cases proportions of sodium sili-
cate and sodium carbonate, if present, may be diminished, for example, to
half the values given above. - ;
The method for manufacture of the agglomerate particles in the de-
sired range of particle sizes requires no more than mixing the finely divided
ion exchanging zeolite builder particles with particles of the water soluble
binder in such a condition as to promote aggregation. Thus, such binder par-
ticles or the zeolite particles may be pre-moistened or otherwise treated
with a solvent material, preferably aqueous and more preferably water, which
will help the binder to adhere to the particles of zeolite and thereby hold
them toeether. In one preferred form of the invention the particles of both
materials are blended together with a fine spray of water or a cloud of steam
being directed onto their moving surfaces, which sufficiently moistens the
binder and dissolves some of it at the surfaces thereof to promote adhesion
of it to a plurality of particles of zeolite. By control of the mixing
speed, the temperature and the proportion of water or other solvent employed,
the extent of adhesion may be regulated and the sizes of particles produced
within a certain time period may also be controlled. Thus, in a preferred
aspect of the invention the nonionic surface active condensate previously de-
scribed, starch, sodium carboxymethyl cellulose, polyvinyl alcohol, poly-
vinyl pyrrolidone or polyacrylamide or a mixture of any or all of these may
be tumbled with the very fine zeolite particles in the presence of moisture,
- 26 -
" . ~
~ ,:
S;~7
e.g., initially from 2 to 30% free moisture, to produce particles of the
desired size and these may be further classified or screened to remove those
outside specification. During the tumbling, especially when anhydrous or
only partially hydrated ion exchanging zeolite is employed or when a hydrat-
able salt is utilized as the binder, free moisture may be removed and the
product may set up so as to be loosely held together in a mass which may be
size reduced to the desired particle size range. Alternatively, a concretion
of the molecular sieve and binder component in water may be created and
after completion of mixing this may be dried, if necessary, and broken up to
desired shape and size. The various particles may be rounded by rolling in a
mill to round off rough edges and the oversize material may be size reduced
to sizes of the desired range, with the undersize materials being reworked.
In another aspect of the invention the molecular sieve and binder may be
mixed together in suitable condition for agglomeration and the agglomerate
may be dried on any of various types of dryers, including drum dryers, film
dryers and tunnel dryers, before being size reduced or classified to the de-
sired size range. In the agglomerating operation desirable adjuvants may be
added, such as perfume, dyes, pigments, etc., to give the agglomerate parti-
cles a desired aroma or appearance, sometimes contrasting with that of the
other detergent particles (the separate particles) but usually being about
the same as them in appearance. Agglomerate particles may also be made by
overspraying tas by spraying dissolved or molten nonionic detergent onto a
moving bed of zeolite particles). Co-spraying and spray drying are also
among methods that are useful. The zeolite particles may be agglomerated as
supplied (in sizes greater than ultimate particle size), may be agglomerated
before being mixed with binder and may be agglomerated with a mixture of
binders, e.g., nonionic detergent plus hydrous silicate builder salt or plus
tripolyphosphate or plus both.
The separate particles are preferably made by spray drying in the
normal manner, such as by spraying a crutcher mix normally containing about
- 27 -
. ~
5347
40 to 70% solids in an aqueous medium, through a narrow orifice, e.g., one of
0.5 to 2 mm. diameter, at a temperature of about 50 to 1~0C. at a pressure of
lO0 to 800 lbs./sq. in. into a drying gas at a temperature of 200 to 500C. to
produce spray dried globular particles having a moisture content which is
usually in the range of about 2 to 12%. Such particles are classified to the
desired particle size range and are merely blended with agglomerate particles,
as in a drum mixer, to produce the desired product. The separate particles
may also be made by other known methods than spray drying, e.g., by drum dry- `
ing, dry mixing, etc.
It is seen that the~methods for the manufacture of the agglomerate
particles and the separate spray dried particles are known, are commercially
feasible and require little special equipment. The products made are free
flowing but if desired, can have additional flow promoting clay or other ma-
terial added to them after or during blending. The products may be used in
the normal manner, as are other household and industrial detergent composi-
tions, and it is found that they do not segregate objectionably on storage or
shipment and usefully and satisfactorily launder soiled clothing without
whitening colors thereof due to any objectionable deposition of zeolite.
The advantages of the products previously mentioned, both the ag-
glomerated ion exchanging zeolite-binder compositions and the ~inal detergent
composition containing such components are obtained when employing either ;
crystalline or amorphous zeolites of the types described but in general, for
many applications, the amorphous material is highly preferred. Thus, even ;
partially hydrated or completely hydrated amorphous material, despite its
normally lower bulk density, e.g., 0.3 g./cc. instead of o.6 g./cc. for a
commercial crystalline molecular sieve zeolite A, can be made into desirable
free flowing builder beads of bulk densities in the range of 0.3 to o.8,
e.g., 0.5 to o.8, and sometimes even higher. Furthermore, the builder beads
and detergent compositions containing them, despite the lower ultimate par-
ticle sizes of the amorphous material (the aggregate sizes, as supplied, may
- 28 -
~i~S~47
be about the same) are dust-free. Comparative testings of the abilities of
the amorphous and crystalline materials to take up binder materials, such as
nonionic detergents show the amorphous zeolites to be far more efficient.
Apparently, the nonionic detergent, in liquid, waxy or greasy form, either in
aqueous medium, melted or otherwise made fluid, when not previously fluid,
penetrates the ultimate amorphous particle or the aggregated amorphous par-
ticle to a significant extent, while not causing the surfaces of such parti-
cles to become objectionably tacky, although the zeolite units can agglomer-
- ate together to the desired particle size. Thus, the finished detergent
builder beads or detergent composition beads may contain desirably large
proportions of nonionic detergent, e.g., 5 to 40%, preferably 5 to 25%, nor-
mally considered to be an objectionable component of detergent beads in such
large quantities because of tackiness and flow problems its presence usually
creates. In effect, the amorphous zeolites very efficiently convert liquid,
waxy or tacky detergents, such as the nonionic detergents previously de-
scribed, to free flowing particulate solid bead form and even hydrated amor-
phous zeolites are surprisingly better in this respect than anhydrous crys-
talline zeolites. The result is that more nonionic detergent can be present
in the detergent composition, with better washing effects and due to the
smaller ultimate particle size of the amorphous zeolite less objectionable
whitening of dark colored laundry results. Furthermore the amorphous zeolite
has better magnesium ion exchanging properties than the corresponding crys-
talline product, important where magnesium hardness problems are encountered.
Various ways of blending amorphous zeolite and anionic detergent are
possible, such as those previously described with respect to detergents and
zeolites generally, but the simplest method is merely to mix the two mate-
rials together and to continue agitation until the product is sufficiently
agglomerated and the detergent-binder is sufficiently sorbed. Of course, in-
stead of using only the detergent as a binder, mixings with other binder ma-
terials present too, e.g., pentasodium tripolyphosphate, sodium carbonate,
- 29 -
1~5347
may also be effected.
In a further improvement of the invention a slurry of anionic deter-
gent, such as a 40 to 70%, e.g., 60%, solids content aqueous slurry of sodium
linear tridecyl benzene sulfonate, containing about 8% of sodium sulfate and
other impurities, is mixed with an equal weight of amorphous ion exchanging
zeolite such as that of previously described Belgian patent 835,351. The ion
exchanging zeolite has a BET surface area of about 50 to 150 square meters
per gram, an ultimate particle size of 0.03 to o.o6 microns, with an aggreg-
ate particle size of 0.2 to lO microns (most of said aggregate being in the 3
to 5 micron range), a density of 2.1 g./cc., a bulk density of 0.3 g./cc., a
moisture content corresponding to about 2.5 to 6 mols H20/mol, an Na20/A1203/
SiO2 molar ratio of 1 : 1 : 2.1 - 2.6, a calcium exchange capacity of 260
to 350 mq. CaC03/q. and a hardness depletion rate residual hardness (mg.
CaC03/gallon) of 0.07 to 0.15 in one minute and less than 0.035 in 10 min-
utes. The mixture of equal weights of both components becomes freely flow-
able and non-dusty within a short period of mixing, e.g., 1 to 5 minutes.
Thus, despite the essentially hydrated state of the amorphous zeolite (con- -~
taining 20% moisture) and the presence of a significant amount of moisture in
the anionic detergent the detergent is made freely flowable without the need
; 20 for drying thereof. The product made may be of satisfactory high density but
low density products can also be produced by various means such as by inten-
tionally mixing gas with the agglomerating materials, as by whipping or use
of an effervescent component.
In another aspect of this invention such an amorphous ion exchang-
ing zeolite, which may already include a moisture content of as much as 30%,
usually including 10 to 25% or more, may be mixed with various other deter-
; gent composition components to produce a free flowing particulate material
from such a mixture of other detergent components, even when some of the men-
tioned components are liquid, and such can be effected without use of heat or
drying equipment. Thus, the product made will very often be more readily
- 30 -
`` il(~S34~^~
soluble in wash water and accordingly will be more efficient in washing be-
cause the various components thereof will start to act very soon after being
added to the wash water, because of rapid particle break-up.
The following examples illustrate the invention but do not limit
it. Unless otherwise indicated, all parts are by weight and all temperatures
are in C.
EXAMPLE 1
A readily disintegrable insoluble detergent builder particulate ag-
glomerate of particle sizes in the 8 to 100 mesh range is made from starch
and type 4A molecular sieve zeolite in equal proportions so that the agglom-
erate produced includes such materials in 1:1 ratio. The starch employed is
; potato starch and the Molecular sieve zeolite is of particle sizes within the
2 to 10 micron ultimate diameter range and of the formula
Nal2(A102 SiO2)12 27H2
~ when completely molecularly hydrated.
J'~ The potato starch is dissolved or well dispersed in water, with the
proportion of water being about equal to that of the potato starch, and the
hydrated molecular sieve zeolite is admixed with the starch-water mix. Dur-
ing this mixing the previously partially hydrated zeolite (20% moisture) is
further hydrated, e.g., to 25% moisture content. Excess moisture is evapor-
ated from the mix during agitation and further moisture is removed by heating
in a tray dryer until the free moisture content is reduced to about 8%. The
agglomerated particles are then size reduced by pressing through a No. 8
screen. Particles that will not pass through the screen are broken up in a
grinder and those which are undersized are recycled back to a mixer in which
additional starch and molecular sieve zeolite particles are being processed.
The molecular sieve zeolite agglomerate made is a free flowing and
form retaining dry solid (containing less than 10% free moisture) but disinte-
grates almost immediately upon being plunged into wash water. Disintegration
into zeolite particles of particle sizes in the 2 to 8.3 micron ultimate
i~S347
particle size range or approaching said range is obtained within about one
minute when the agglomerate is added, with agitation, to wash water at 70C.
in an automatic washing machine and such dispersion is obtainable within
about 2 minutes at lower temperatures, e.g., 10C. Thus, when employed with
complementary particulate synthetic organic detergent and builder or filler
materials a built synthetic detergent washing medium is produced which is
quickly and maximally effective as a detergent because the zeolite is quickly
available for its calcium exchange function. Also, the insoluble zeolite
molecular sieve particles are in such small form that they are not entrapped
in openings in the weaves of fabrics being laundered, even if said laundry is
line dried or hanger or drip dried, rather than machine dried.
Instead of following the process described above, in a variation
thereof the zeolite particles and starch particles are tumbled together in a
Day mixer and alternatively, in a Lodige mixer until well blended, after
which time 8% of water, by weight of the total of zeolite and starch charged,
is sprayed onto the tumbling particles and it is noted that they agglomerate
into larger, fairly uniformly sized particles, in the 4 to 180 mesh range,
which are then classified to particles of 8 to 100 mesh, which are free flow-
ing and non-caking on storage. In still another variation of the manufactur-
ing method the same formula and the immediately preceding method are employed
but instead of screening the particles, etc. after agglomeration, agglomera-
tion is halted at a stage in the process when the particles are substantially
within the desired particle size range, 8 to 100 mesh, after which the beads
resulting are classified so that all are within the 8 to 100 mesh diameter
range. A portion of such product is then blended with an equal weight of
sodium perborate beads of diameters in the mentioned range for use as an ad-
ditive to other detergent components, preferably in spray dried form, to pro-
duce a bleaching detergent containing zeolite builder.
EXAMPLE 2
The procedures of Example 1 are repeated but with the different
- 32 -
5347
agglomerate formulations given herein:
A) 25% of corn starch and 75% of 5% hydrated zeolite 4Aj
B) 75% zeolite X, anhydrous, and 25% of a 50:50 mixture of poly-
vinyl pyrrolidone and polyvinyl alcohol;
C) 85% of zeolite 4A and 15% of sodium carboxymethyl cellulose;
D) 50% of zeolite 4A and 50% of corn syrup starch.
The percentages of moisture in the products of Experiments A, B and
C are increased and decreased 50% in both cases compared to those of Example
1 and in Experiment D no more than 10% (usually 0% of added moisture is em-
ploye~. The products resulting are useful builder agglomerates having thedesired properties mentioned for the products of Example 1.
EXAMPLE 3
Particulate agglomerate insoluble builder beads are made by agglom-
erating in an inclined tube mixer, rotating at 30 revolutions per minute, the
following mixtures, all in the presence of an additional 15% of moisture,
sprayed into the mixer during the mixing operation. Sufficient agglomeration
! iS obtained within 5 to 10 minutes, as in the experiments of Examples 1 and
2. The products made are sufficiently free flowing and non-tacky so that
they can be employed as builder additives for use with other components to
produce complete heavy duty built detergent compositions which do not objec-
tionably whiten colored laundry.
E) 50% zeolite 4A and 50% pentasodium tripolyphosphate,
F) 50% zeolite 4A, 25% pentasodium tripolyphosphate and 25% corn
starch;
G) 50% zeolite 4A and 50% Neoaol* 45-11 (condensation product of
higher fatty alcohol averaging 14 to 15 carbon atoms per mol with about 11
mols of ethylene oxide);
H) 50% of zeolite X, anhydrous, 25% of Neodol* 45-11 and 25% of
potato starch;
I) 50% of zeolite 4A (10% hydrated), 20% of sodium silicate
*Trademark - 33 -
. --
5347
(Na20:SiO2 = 1:2.4), 10% of sodium carboxymethyl cellulose and 20% of corn
starch;
J) 50% of zeolite 4A (15% hydrated), 25% of Na2S04 and 25% of
3 5 lO
In similar experiments 0.3% of perfume and 0.81 optical brightener
are also present in each formula, replacing 1.1% of the zeolites.
EXAMPLE 4
The compositions of Examples 1-3 are varied in proportions so that
the contents of zeolites are 30%, 50% and 70%, respectively, in each case,
with the pe~centages of other constituents being proportionally adjusted ac-
cordingly. The products made are useful particulate agglomerate builder
beads, suitable for addition to beads of complementing detergent composition
components to make heavy duty built synthetic organic detergents which no not
objectionably whiten dyed fabrics washed with them and line dried. When, in
such products, the mentioned zeolites are replaced by mixtures of zeolites,
e.g., 50:50 mixtures of zeolite 4A and zeolite X, anhydrous, partially hy-
drated or completely hydrated, useful builder agglomerate particles are also
produced. Similarly, when in place of zeolite 4A and/or zeolite X (zeolites
Y and L may also be substituted) there are employed those of the previously
mentioned Austrian, German and United States patent applications, acceptable
products of improved characteristics are also produced, which act faster to
tie up calcium ion in the wash water and deposit less insoluble zeolite build-
er on laundry being washed than results from spray drying the complete formu-
lation.
EXAMPLE 5
A spray dried detergent composition of particle sizes in the 8 to
lO0 mesh range is made by spraying into a countercurrent tower having drying
air at a temperature of 250 C. passing through it, a 65% solids content aque-
ous crutcher mix at a temperature of 70 C. and a spraying pressure of about
400 lbs./sq. in., through spray nozzles of l mm. dia. The holdup time in the
- 31~ -
`5;~47
spray tower is long enough, usually being about five minutes, to dry the
beads to a moisture content of about 11%. The beads produced are of the for-
mula: -
Constituents Percentage
Sodium linear tridecylbenzene sulfonate 15
Pentasodium tripolyphosphate 32
Sodium sulfate 31.8
Sodium silicate (Na20:SiO2 = 1:2.35) 7
Polyethoxylated alcohol (Neodol 45-11) 1
Borax (as Na2B47 10 H20)
Preservative 0.01
Sodium carboxymethyl cellulose 0.3
Perfume 0.2
~3 Fluorescent brighteners (mixture) 0.7
Moisture 11
With the above described spray dried separate particles of the de-
~ tergent composition are separately admixed sufficient of the various agglom-
;~l erates described in Example 1 to produce a plurality of detergent products,
each containing 20% of the zeolite. 20% Zeolite content is a preferred per-
centage but sueh amount is modified so as to also produce the corresponding
products containing 10% and 30% of the molecular sieve zeolites. Soiled,
mixed laundry, including cotton and polyester-cotton blend fabrics soiled
with clayey, carbonaceous and oily materials, are washed in 150 p.p.m. hard-
ness (3:2 Ca :Mg hardness, as CaC03) at 0.15 and 0~25% concentrations in
wash water at washing temperatures of 30 , 50 and 70C. and such washings
result in good cleanings of the laundry when using the automatic washing cycle
of conventional top loading and side loading household automatic washing ma-
chines. Particularly important is the low deposition of the insoluble builder
on dyed fabrics being washed, especially on light blue dyed percale which is
line dried, considered to be an extreme test of such deposition. The products
- 35 -
,.. ", . , .. - . ...
5347
described, heavy duty detergents containing readily disintegrable agglomerate
particles of molecular sieve zeolite builder, are of acceptable properties
for a commercial product, being sufficiently free flowing and non-caking on
storage to meet with acceptance by the normal user thereof and quickly se-
questering hardness ions in wash waters to promote cleaning, while still not
depositlng objectionably on dyed materials. When the other agglomerate par-
ticles of Examples 2-4 are substituted for those of Example 1 in the built
detergent compositions described in this example similar acceptable results
are obtained. This is also so when for the eodium linear alkyl benzene sul-
fonate of the formula there are substituted the olefin sulfonate, paraffinsulfonate, ethoxylate sulfate and other anionic detergents previously de-
scribed and when the different binders and combinations thereof mentioned are
employed in the same and different amounts within the ranges given.
EXAMPLE 6
The experiments of Example 5 are repeated but instead of using the
phosphate-containing detergent composition for the separate particles a non-
phosphate detergent of the following formula is used instead (final product
formula given).
I Constituent Percentage
Sodium linear dodecylbenzene sulfonate20
Zeolite 4A (20% hydrated) 25
Potato starch 9
Sodium carboxymethyl cellulose
Sodium carbonate 13
Sodium sulfate 15
Moisture 5
- Adjuvants (perfume, colorant, optical brighteners, 5
flow promoting agent, bactericide,
; stabi]izer)
Sodium silicate (Na20:SiO2 = 1:2.4) 7
The zeolite, carbonate, starch and half the CMC are in the agglom-
- 36 -
æ
~l~S347
erate particles, with the other materials being in the separate beads.
Although in the absence of the phosphate the detergency is not as
good as it is for the products of Example 5 cleaning results obtained are ac-
ceptable and are better than when the molecular sieve zeolite is omitted from
the formula. When changes are made in the molecular sieve zeolite and the
binder materials and when the proportions of some of the materials are altered
between the agglomerate particles and the separate particles (usually keeping
the carbonate with the agglomerate particles) within the described scope of
this invention good detergents of acceptable washing and non-deposition char-
acteristics result. Thus it is established that non-phosphate detergents of
1 satisfactory cleaning powers can be made without having the insoluble molec-
ular sieve zeolite unsatisfactorily deposit on colored materials. The prod-
ucts made are non-segregating when sub~ected to storage and shipment. They
are also non-dusting (as are those of the previous examples).
In variations of the product of Example 6, to 100 parts of the fin-
ished product are added ~0 parts of sodium perborate or 30 parts of sodium -
perborate plus 0.5 part of suitable activator for the perborate and washing
and bleaching are effected in the washing machine at elevated temperature
(e.g., ôO C.). In such cases good washing and bleaching of hard tO remove
stains such as red wine, coffee, tea and cocoa are obtained, especially with
the activated perborate bleach and similar results are obtained when instead
of the perborate an equivalent amount of percarbonate or activated peroxymono-
sulfate is employed. An additional advantage of the present invention in the
case of bleaching detergent compositions is in the apparent sorption by the
finely divided molecular sieve zeolite of any fugitive dye released by the
colored laundry, preventing it from redepositing on white articles laundered
with the colored materials. In another modification of the formula, instead
of perborate, capsules of sodium bicarbonate and citric acid are employed,
with such reactive solids being maintained separate from one another and dry
so that they interact only when the capsules are broken on being plunged into
_ 37 _
~1~53~7
water. Such capsules are preferably utilized with the agglomerate particles
but may be mixed with the agglomerate and/or separate particles providing
that they are of about the same particle size so as to prevent settling.
They effervesce and promote rapid breakup and mixing of the components of the
composition. Of course, in built alkaline compositions, when carbonate is
present, the citric acid or other acidifying agent should be maintained close
to the bicarbonate so as to be able to react with it to generate carbon diox-
ide gas before the acid is neutralized by other alkali in the wash water.
When alkaline builders are omitted from the detergent composition the dry re-
active effervescing ingredients may be separately present in the different
beads (one in the agglomerate and the other in the separate beads).
In still other modifications of the product, instead of being pro-
duced in bead form, flakes or granules of the components may be made, in which
cases the products are equally good as detergents and in not depositing molec-
ular sieve zeolite on washed laundry although flow characteristics are not
quite as good. Builders other than the zeolites may be omitted and anhydrous
sodium sulfate in the agglomerate and/or separate particles may be hydrated
in the manufacture of the product to remove excess free moisture.
EXAMPLE 7
The experiments of Examples 1-6 are all repeated but instead of the
crystalline zeolites utilized therein there is substituted an amorphous zeo-
lite of the type described in Belgian patent 835,351. The material utilized
is obtained from J. M. Huber Corp. and is of the formula given at page 11 of
this specification and of the properties described at pages 36 and 37. In
; other variations of the formulas of Examples 1-6 half of the crystalline zeo-
lite is replaced by said amorphous zeolite. The final products made are of
detergencies like those of the corresponding final compositions of Examples
1-6 and are considered to be more effective in hard waters containing substan-
tial proportions of magnesium hardness, in addition to calcium hardness. The
products are dryer, especially the amorphous zeolite-binder builders, are
,~
~5347
more free flowing, less inclined toward tackiness and are also dust free.
Also, less deposition of the insoluble zeolite on washed dark colored laundry
results, even when washing is effected in cold water and the laundry is line
dried, probably due to smaller sizes and more rounded configurations of the
amorphous particles. Especially when nonionic detergents are employed as
binder materials the builder particles of this invention are made of a wide
variety of bulk densities, including those within the range of 0.3 to o.8
g./cc. and even higher, depending on binder and moisture contents and mixing
times. In some instances, due to the sorbing power of the amorphous zeolites
described additional moisture will be employed in the formulas of Examples
1-6, as modified for the purpose of this example. Thus, especially when
; moisture contents of the amorphous zeolites are lower than 30%, e.g., 10, 20
and 25%, rather than 30% as is present in the Huber zeolite mentioned, more
water, about 1.5 times the amount previously described, will be used in mak-
ing the starch-water mixture of Example 1 and any subsequent drying steps may
be omitted.
Utilizing the amorphous zeolite modifications of this example allows
substantial disintegration of the zeolite-binder particles into zeolite par-
ticles of ultimate particle sizes in the 0.03 to o.o6 micron size range with-
in about a minute after the agglomerate is added into the hot wash water with
agitation.
In the alternative processes of Example 1 instead of utilizing 8%
of water in the spray, as much as 30% may sometimes be employed, with the
preferred range being from 10 to 25%. In the modifications of the rest of
the examples moisture contents described therein may be employed but normally
such contents are increased by amounts from 10 to 50% thereof because the
amorphous zeolite is being used.
In further variations within this example the amorphous and mixed
amorphous-crystalline ion exchange zeolites of the United States patent
applications identified by attorney's docket numbers 2001, 2003 and 2002,
- 39 -
X~ .
5347
,...
described at pages 10 and 11 of this specification, are employed instead of
the Huber amorphous zeolite and the water content employed is adjusted, as
was described for formulas including the Huber zeolite. The products result-
ing are good builders and the final products are free ~lowing, non-tacky,
satisfactory detergents which do not objectionably whiten dark colored
laundry.
The products of Example 7 (and also of Examples 1-6) which contain
alkaline builder salts such as sodium carbonate or sodium tripolyphosphate
will usually have a pH in the range of 9 to 11, preferably 9.5 to 10.5 where-
as those builder particles containing no alkaline material except for thezeolite will usually have a pH within the 7.5 - 10 range, normally 8 - 9.5.
Thus, the detergent composition pH's will be in the best range for good wash-
ing and suitable mildness to the materials being washed and to the hands of
the user and, if desired, the binder particles may still be of sufficiently
high pH to facilitate washing. Such pH's will generally be from 7.5 - 11,
preferably 9.5 - 10.5.
Although the amorphous compositions are superior to those contain-
ing only crystalline zeolites of the types described, such superiority is
most significant in the cases wherein nonionic surface active agents or
builder salts or mixtures thereof are employed as binders. The builder par-
ticles so made and the detergent compositions including them are the best
commercially feasible products and a large measure of their acceptability is
due to the use of amorphous, rather than crystalline zeolites.
EXAMPLE 8
In an extension of the concept of this invention, arising out of
the discovery of the unusual beneficial effects of the amorphous zeolite in
improving the properties of detergent compositions in which it is incorporat-
ed in place of crystalline zeolite as an insoluble builder, it was discovered
that good detergent compositions could be based essentially on only synthetic
organic detergent, such as an anionic or nonionic detergent and the amorphous
- 40 -
'X! .
- \
ll~S347
;
zeolite, preferably with an alkalizing agent such as alkaline builder salt,
e.g., sodium carbonate, pentasodium tripolyphosphate, also being present.
Such materials are described in this example.
Percent
Neodol* 45-11 (100% active ingredient) 50
Amorphous zeolite (type described in Example 7, 50
manufactured by
J. M. Huber Corp.)
The zeolite powder lS added with stirring to the waxy nonionic
detergent at a temperature of about 30C. (but similar mixings are effected
at temperatures of 20 C., 25C. and 35C. or higher and while mixing is tak-
ing place the waxy nonionic becomes sorbed by the zeolite particles, despite
its considerable viscosity, producing a powdered composite which is free flow-
ing and of desired particle size in the 4 to 180 mesh range. This material ~ ;
is classified and product in the 8 to 100 mesh range is separated and tested
as a detergent. It is a good detergent, washing soiled clothes satisfactori-
ly in laboratory and practical laundry tests. It does not objectionably
whiten dark colored items nor does it make then stiff or boardy. The product
is free flowing and maintains this characteristic on storage. Its bulk den-
sity is in the 0.4 to o.6 g./cc. range but this is then increased and agglom-
eration into larger particles is then effected by further mixing, especially
using a water spray in amount from 10 to 30% of the weight of the final
product.
In variations of this experiment Neodol 25-7 is substituted for
Neodol 45-11 and similar results are obtained. Desirably, when the nonionic
detergent is the only active synthetic organic detergent ma+erial present the
proportion thereof in the final composition will be from 10 to 60%, preferably
20 to 50%.
In another variation of this example a slurry of anionic detergent
is converted to free flowing powdered form.
*Trademark - ~1 -
.~ .
- \ r
11~53~3L7
Sodium linear tridecyl benzene sulfonate slurry 50
- (60% active ingredient, 9% sodium sulfate
and other impurities and 31% water)
Amorphous zeolite (as above) 50
The powdered amorphous zeolite is admixed with the aqueous slurry
of anionic detergent and soon, within five minutes, free flowing particulate
product results, of the particle sizes previously mentioned. It is classi-
fied or further agglomerated to a desired 8-100 mesh range of particle sizes
and is tested and found satisfactory as a detergent, cleaning laundry well
and not objectionably depositing insoluble white particles thereon. Clearly,
an advantage of this process is in energy conservation because the use of a
spray drying tower is not required to manufacture a flowable particulate
solid product.
In both the nonionic and anionic formula processes described in
this example 10, 20, 30 and 40 parts of pentasodium tripolyphosphate, sodium
carbonate or an equal mixture thereof are also utilized with 100 parts of the
formulas previously given, the soluble builder salt being present pre-mixed
with the zeolite or post-mixed with the zeolite-detergent powder. Improved
detergency results due to the presence of the additional builder and flowab-
ility and other physical properties are also satisfactory.
In a further variation of this experiment the other amorphous zeo-
~` lites previously mentioned are utilized and satisfactory results, comparable
to those previously described, are obtained.
In comparative examples wherein type A molecular sieve zeolite(crystalline) is employed in place of the amorphous zeolites described the
products resulting are pasty and never become satisfactorily flowing.
EXAMPLE 9
This example illustrates an aspect of the invention discovered
after the excellent building and flow improving effects of the described
amorphous ion exchanging zeolites were noted. In the formula given commer-
cially acceptable non-dusting, non-tacky free flowing, useful heavy duty
- 42 -
~' ":'I
'
11C~5347
detergents are produced, which may, if desired, be low in phosphate content
or free thereof. Such products may be manufactured at desirable comparative-
ly high bulk densities, making it possible to market them in smaller packages
and may be based on hitherto unacceptably sticky nonionic detergents (unac-
ceptable in comparatively large proportions, e.g., 10 or 15 to 50%).
- 43 -
`` 11(~5347
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- 44 -
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- . . - . , .. ., , -:
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11~5;34~
The various constituents listed are mixed together in powdered
form, such powders usually being of mesh sizes in the range of 8 to 325,
United States Standard Sieve Series, and are sufficiently mixed so that the
synthetic organic detergent is dispersed and it and any other waxy or sticky
materials which may not be in powder form are sorbed or otherwise made free
flowing by -the amorphous zeolite and other powdered constituents present.
All the products resulting which contain nonionic detergent are free flowing,
non-tacky, dust-free detergent powders and all possess satisfactory washing
properties for a built synthetic organic detergent.
To diminish any dusting of the present compositions, particularly
those containing anionic synthetic organic detergent, the various components
thereof, except for heat-sensitive materials such as the sodium perborate
tetrahydrate, may be spray dried and the heat sensitive compounds may be
post-added. The compositions based on nonionic synthetic organic detergent
may also have a portion thereof spray dried initially and then blended with
a mix of the balance of the material. For example, in formulation 1, the car-
bonate, silicate, CMC and sodium sulfate may be spray dried together to form
beads of particle size in the 4 to 180 mesh range, which are then blended
with a previously made mixture of Neodol*25-7, amorphous zeolite and sodium
perborate tetrahydrate or the Neodol*25-7 may be sprayed onto a tumbling mass
of the other materials. It is noted that the absence of sodium linear tri-
decyl benzene sulfonate from the spray dried component makes it a better sor-
bent for the nonionic detergent. In all formulas, other adJuvants, such as
perfumes, colorants, enzymes, may be post-added. They may be incorporated in
crutcher mixes before spray drying or with other components being pre-mixed.
In some cases, portions of the components may be spray dried and other por-
tions of the same components may be pre-mixed with other materials, with the
two or more parts then beine mixed to make a final product.
It is noted that the products made are of bulk densities in the
range of 0.5 - o.8 g./cc. but products of bulk densities in the 0.3 to 0.9
~Trademark - 45 -
: :...... . . -
53~7
range are also obtainable. It is also observed that the presence of nonionic
detergent tends to increase the bulk density of the product, compared to com-
positions wherein anionic detergent is employed. Bulk density may be adjust-
ed by using more or less of spray dried materials, with greater quantities
thereof lowering the bulk density.
It is seen from the formulations given that satisfactory comparat-
ively high bulk density detergent powders can be made of satisfactory flow
and detergency characteristics without the use of phosphates, by employing
amorphous zeolite as a builder, preferably with nonionic, rather than anionic
detergent.
The products containing amorphous zeolite are superior in magnesium
exchanging capability to those containing similar proportions of crystalline
zeolite (molecular sieves) and are less apt to deposit objectionably on dark
colored laundry. Other builder salts than the zeollte are desirable compon-
ents of these compositions but they are not required, although silicates are
usually desirably present, especially for their anti-corrosion properties.
If desired, supplementary organic builder may be utilized, such as citrates,
gluconates, trisodium carboxymethyloxysuccinàte, and Monsanto's Builder M,
trisodium-2-oxa-1,1,3-propane tricarboxylate. Normally the products result-
ing will have a pH in the range of 8 to 11, preferably 9.5 to 10.5 and par-
ticle siz,es will be from 10 to 200 mesh. Yet, despite the fineness of the
particles they are non-dusting and free flowing, capable of being poured from
a narrow-necked bottle or similar container. (With crystalline zeolite being
used instead of amorphous zeolite the product is not as free flowing, espe-
cially when it also contains waxy or pasty nonionic detergent.
Results like those reported are generally obtainable when the con-
tent of the nonionic detergent is in the range of 10 to 60%, preferably 20 to
40% and that of the amorphous zeolite is in the same range, with the propor-
tions being complementary or less than complementary. Proportions of water
soluble builder salt will generally be from 10 to 50%, preferably 15 to 40%.
- - 46 -
11(;~5347
The ratio of nonionic detergent : amorphous zeolite is in the range of 1:3
to 3:1, preferably 1:2 to 2:1 and that of amorphous zeolite : water soluble
builder salt is infinity to 1:4, preferably 3:1 to 1:3. When crystalline
zeolite is also present, e.g., at 10 to 60%, the ratio of its content to that
of amorphous zeolite is 6:1 to 1:10, preferably 3:1 to 1:3. Free moisture
will normally be less than 15%, preferably less than 10~ and most preferably
less than 5~, to promote flowability. However, the zeolites do contain addi-
tional water of hydration, with such content normally being about 20% for the
crystalline material and 20-30% for the amorphous material. When crystalline
zeolite is present the proportion of total zeolite may be increased to as
much as 80% but preferably this will be held to 60% or less.
Results similar to those reported for this example are also obtained
when the amorphous zeolite or amorphous-crystalline zeolite mixtures used are
replaced by the other such materials mentioned in this specification and when
other mentioned nonionic detergents and builders are substituted.
By means of the present invention there is obtained a non-dusting,
desirably sized, non-segregating, attractive detergent composition containing
synthetic organic detergent and ion exchangine zeolite builder which washes
effectively and which possesses significant advantages over similar spray
dried formulations, especially with respect to absence or diminution of de-
positing of zeolite on colored fabrics that are laundered and line dried.
However, the invention is also additionally useful because there is produced
a particulate zeolite builder agglomerate which can be added, as desired, to
the balances of the spray dried detergent formulations, wherein it promotes
flowability and contributes the building effect of the ion exchanging zeo-
lite. Keeping the zeolite separate from the bulk of the detergent formula-
tion allows ready adjustment of such formulation to include more or less of
the zeolite builder, as may be desired, and thus gives greater flexibility of
manufacturing plant operation. Required tower throughput, sometimes a bot-
tleneck in production, is lowered and sometimes is nil, allowing greater
- 47 -
as~
production rates. While changings of the spray dried formulas to allow mod- -
ifications of the end products, as in changing phosphate contents from 35%
STPP to 25%, 15% or 0%, may be effected by changing tower operations and mod-
ifying the proportion of agglomerate particles used, in some instances the
formula may be modified merely by changing the proportion of agglomerate par-
ticles employed and/or the types of agglomerates used. In those instances
wherein nonionic detergents or anionic detergent slurries are "solidified" by
use of amorphous zeolite, detergent - builder products are made without the
need for any spray drying at all and use of the amorphous zeolites in such
products further diminishes any tendency to whiten dark colored laundry with
the detergent compositions.
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, with the present specification before
him, will be able to utilize substitutes and equivalents without going out-
side the scope of the in~ention.
- 48 -
, ~
