Note: Descriptions are shown in the official language in which they were submitted.
6~3
FR~E FLOWING PARTICULATE D~T~RGENT COMPOSITIONS
_CONTAINING A NORM~LLY TACKY DETERGENT
This invention ~elates to particulate detergent mixtures
or compositions and more particularly, to such compositions con-
taining water soluble organic surface active agents, such asdetergents. More particularly, it relates to free 10wing non-
tacky par iculate detergents containing normally tacky synthetic
organic detergents.
The use of many organic surface active agents (hereafter
referred to as surfactants) in solid detergent products, such as
laundry washing powders, has been impeded because those detergent
compounds have heretofore been available only as tacky or sticky
pastes or solids, at room temperature, which are difficult to
handle or to admix with other ingredients of conventional
detergent formulations, e.g., builder salts. The tacky character
of suçh detergents may be attributed in some cases to the
presence therein of minor proportions, such as about 0.1 to 30%
of water, oi~l or of products of the manufacture of the materials.
In other instances, particularly, in the case of anionic
detergents or surfactants of the paraffin sulfonate type, the
tacky consistency appears to be an inherent-disadvantageous
property of the pure detergent.
The aforementioned disadvantages of the prior art,
normally tacky, organic surfactants are overcome by the present
invention, which is of a free flowing pulverulent detergent
mixture comprising a particulate molecular sieve zeolite and a -
normally tacky water sbluble organic surfactant, usually in a
' . '
V~i~6~7~
weight ratio of about 20:1 to about 0.5:1. The invention also includes a
process for converting a normally tacky water soluble organic surfactant to
a free flowing or more freely flowing powder or particulate product which
comprises intimately mixing the surfactant and the zeolite molecular sieve
in the above-stated proportions.
Thus, according to one aspect, the invention provides a free flow-
ing particulate detergent composition in the form of particles consisting
essentially of a substantially homogeneous mixture of a finely divided water- '.
insoluble crystalline aluminosilicate zeolite having an A12O3SiO2 mole ratio
of 1:2 to 1:5, a moisture content of from 1% to 36%, a ne$work of substantial-
ly uniformly sized pores in the range of about 3 to lO Angstroms, a particle
size of 5 to 9 microns, calcium ion sequestering properties and a cation .~
which is selected from the group consisting of sodium potassium, lithium, :
ammonium and hydrogen; and a normally tacky water-soluble organic surfactant .
selected from the group consisting of anionic, nonionic, cationic and ampho- :. - .
teric surfactants in a weight ratio of zeolite to surfactant of 20:1 to about :.~ ~.
0.5:1. . ~,~
According to a further aspect, the invention provides a process ~ ~ .
for converting a normally tacky water-soluble organic surfactant selected
from the group consisting of anionic, nonionic, cationic and amphoteric sur- .~ .
factants to a free-flowing non-tacky powder which comprises intimately mixing
for 1 to 20 minutes at a temperature in the range of 5 to 90C. a finely di- . : :
vided, water-insoluble, crystalline aluminosilicate zeolite having an A1203 ~ . .
to SiO2 mole ratio of 1:2 to 1:5, a moisture content of from 1% to 36%, par-
ticle size of 5 to 9 microns, calcium ion sequestering properties and a cation :~ ~
which is selected from the group consisting of sodium, potassium, lithium, . ~ .
ammonium and hydrogen and a network of substantially uniformly sized pores in ~
the range of 3 to about 10 Angstroms, with said surfactant, employing about ~ ;
0.5 to 20 parts of a molecular si.eve zeolite per part of the surfactant to . ~ .
form a homogeneous pulverulent product. . ;
',,~ .
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f.''''' ~'' "
The free flowing pulverulent mixture of zeolite molecular sieve
and normally tacky surfactant is obtained by mixing together the components
thereof, as by stirring, shaking or otherwise agitating together the mole-
cular sieve zeolite and the surfactant for a short period, normally about 1
to 20 minutes, advantageously 5 to 15 minutes. Usually mixing of the zeolite
and surfactant will be carried out at about room temperature, e.g., about
20 to 35C., but if desired, mixing can be effected at temperatures in the
range of about 10 to ~0C. and even at 5 to 90C. Other temperatures may be
used providing that the materials mixed are stable thereat. Generally, the
zeolite and surfactant can be mixed in any suitable vessel, for example, a
tumbling drum, barrel, or jar, or the shipping container used for shipping
the normally tacky organic surfactant. They may be mixed in size-reducing
and blending apparatuses, too. Agitation of the molecular sieve zeolite
organic surfactant may be fast, slow or medium and can be supplied by any
suitable stirring, shaking or size-reducing apparatus, such as a blender
(preferably of the twin-shell type), shaker, vibrator, micro-pulverizer, ~ -
grinding mill or rollers for rotating the mixing vessel or container. The
sticky surfactant and molecular sleve
~ ~'
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zeolite can also be mixed in a conventional agitated soap or
detergent mixing vessel, such as a soap or detergent crutcher.
The resulting intimate mixture of molecular sieve
zeolite and organic surfactant is a free flowing pulverulent
mass of excellent stability. It does not separate or become
sticky or tacky even on storage. The free flowing pulverulent
surfactant composition of the invention can thus be handled,
transported and dry mixed with conventional solid composition
component detergents and adj u vants,such as builder salts,
fillers, anti-redeposition agents, colorants, foaming and anti-
foaming agents, etc., with far greater ease than is the case
with the original tacky, sticky organic surfactant. Even in
those cases where an insufficient quantity of molecular sieve
zeolite is used, so that completely satisfactory flow properties
15- are not obtained, such properties are substantially improved.
The aforementioned ease of mixing the present molecular
sleve zeolite-surfactant compositions with other detergent
additives avoids the tedious necessity of mixing the surfactant
and other de~ergent adjuvants in aqueous media and thereafter
drying the aqueous mixture in order to prepare particulate
solid laundry detergent formulations. However if it is desired,
to obtain the final particulate laundry detergent formulation
in a particular form or shape, e.g., hollow beads or granules,
the molecular zeolite-surfactant mixture and the detergent
adjuvants can be mixed in an aqueous medium and the aqueous
dispersion or solution resulting can thereafter be dried at
elevated temperature, as in a spray drier, preferably
~.~63..~
cour~ercurrentlywith hot air according to spray drying techniques
which are conventional in the detergent art.
The molecular sieves utilized in the invention are
water insoluble crystalline, aluminosilicate zeolites of natural
or synthetic origin which are characterized by having a network
of similarly or substantially uniformly sized pores in the range
of about 3 to 10 Angstroms, which size is uniquely determined by
the unit structure of the zeolite crystal. Of course,zeolite
molecular sieves containing two or more such networks of different
siæed pores can also be employed.
The molecular sieve zeolite should also be a univalent
cation exchanging zeolite, i.e., it should ba an aluminosilicate
of a univalent cation such as sodium, potassium, lithium (in
suitable cases) or other alkali metal, ammonium or hydrogen.
Preferably, such univalent cation is an alkali metal cation,
especially sodium or potassium.
Preferred crystalline types of zeolites utilized as
- molecular sieves in the invention are zeolites of the following
~.
crystal structure: A, X, Y, L, mordenite, chabazite and erionite
and other molecular sieve zeolites disclosed in Table 9.6 of
the Breck text, m~ntioned below. Generally preferred are the
molecular sieve zeolites with A12O3:SiO2 molar ratios of 1:2
to 1:4. Mixtures of these and equivalent molecular sieve
zeolites can a1so be used. These preferred crystalline struc-
- 25 ture types of zeolites are well known in the ion exchange art
and are more particularly described in the text, "Zeolite
Molecular S_ ves", by Donald W. Breck, published by John Wiley
& Sons in 1974. Most preferably the molecular sieve zeolite
,~ _
.
673
used is a synthetic molecular sieve type A crystalline zeolite,
which is more particularly described on page 133 of the afore-
mentioned Breck reference. Best results are generally obtained
using a Type 4A molecular sieve zeolite wherein the univalent ~
cation of the zeolite is sodium and the pore size of the zeolite
is about 4 A (nominal). These especially preferred zeolite
molecular sieves are described in U.S. patent 2!882,243 which
refers to them as zeolite A.
Molecular sieve zeolites can be prepared in either a
dehydrated, calcined form which contains up to about 3~ of
moisture, e.g., 1 to 3~, or in a hydrated, i.e., water loaded
form which contains additional adsorbed water in an amount up
to about 36%, e.g., 4 to 30~,depending on the type of zeolite used.
Preferably the dehydrated form of the molecular sieve is employed,
usually containing about 2% of water. The manufacture of such
crystals is wall known in the art and they may be obtained
commercially from various manufacturers, including Henkel & Cie.
and Union Carbide Corporation. In the preparation of zeolite A,
referred to abo~e, the hydrated zeolite crystals that are formed
in the crystallization medium (such as a hydrous amorphous
sodium aluminosilicate gel) are dehydrated or calcined, accord-
ing to the normal practice in preparing crystals for use as
catalysts, e,g., cracking catalysts. The hydrated form of
zeolite, either completely hydrated or partially hydrated, can
be recovered byfilte~ing off the crystals from the crystallization
medium and drying them in air at ambient temperature, without
... : , .. . .
-
calcining, so that their water content is in the range of about
4 to 30~, e.g., 20 to 28.5% and such zeolites can be used,too.
However, it appears that the drier zeolites improve flowability
of the detergent to a greater extent than the zeolites that
contain more water, possibly because more pores thereof are "open".
The crystalline molecular sieve zeolitesused are
usually also substantially free of adsorbed gases, such as
carbon dioxide, since such gas-containing zeolites may produce
undeslrable foaming on contact with water. Preferably the
molecular sieve zeolite should be in finely divided condition,
~uch as crystals 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 microns. The sieves of 5.9 to 6.4
microns are generally better detergent builders, in addition to
their anti-caking and flow promoting properties.
Water soluble organic surfactants which are normally
tacky or sticky can be found in all of the principal surfactant
categories, among water soluble organic surfactants of the anionic,
nonionic, cationic and amphoteric types. These categories are
more particularly described in McCutcheon's De~ergents and
mulsifiers, 1969 Annual and by Schwartz, Perry and Berch,
Surface Active Agents, Vol. II (Interscience Publishers 1958~.
The present compositions may include such tacky or poorly flowing
or caking detergents which are inherently tacky or contain oil,
water, wax, solvents or other liquids which tend to make them
tacky. Such additional tackifying agents are usually only a
minor proportion, ~.g., 0.1 to 10%, the surfactant.
.
-- 6
.
.
..,
.
~6~ 73
Suitable anionic surfactants lnclude hlgher (10 to 20
carbon atom) alk~l benzene sulfonate salts wherein the alkyl
group pre~erably contains 10 to 16 carbon atoms. The alkyl
group is preferably a straight chain alkyl radical of about 11
to 13 or 14 carbon atoms. Preferably~ the alkyl benzene sul~onate
has a hlgh content of 3- (or higher) phenyl is~mers and a
correspondingly low content (well below 50~) of 2- (or lower)
phenyl isomers; in other terminology, the benzene ring is prefer-
ably attached in large part at the 3 or higher, eOg.~ 4, 5~
6 or 7 position of the alkyl group and the content of isomers
in whlch the benzene ring is attached at the 2 or 1 position is
correspondingly low, Typlcal alkyl benzene sulfonate surfactants
are described ln the patent literature.
A1SQ typical of anionic surfactants are olefin
sulfonate salts. Generally they contain long chain alkenyl
sulfonates or long chain hydroxyalkane sulfonates (with the OH
being ~ carbon atom which is not directly attached to the
carbon atom bearing the -S03 group). More usually, the olefin
sulfonate detergent comprises a mixture o~ these two types of
compoundæ in varying amounts~ often together with long chain
disulfonates or sulfate-sulfonates. Such olefln sulfonates are
described in many patents and in the article by Baumann
et al. in ~ette-Seifen~Anstrichmittel 72~ No. 4, pp. 247 253
(1970). The above-mentioned dlsclosure ls incorporated here-
in by reference. The number of carbon atoms in the olefin
sulfonates is usually within the range of lO to 25~ more commonly
.. . . . .. . . . . . . . .
7~ ~
12 to 0, e.g., a mlxture o~ principally Cl~, C14 and C16,
having an average of about 14 carbon atoms or a mixture of
p ipally C14, C16 and C18, having an average of about 16
carbon atoms.
Another class of water soluble organic anionic
surfactants is that of the higher (10 to 20 carbon atom) paraffin
sulfonates These may be the primary para~fin sulfonates made
by reacting long chain alpha olefins and bisulfites, e.g., sodium
bisulfite, or paraffin sulfonates having the sulfonate groups
d1stributed along the paraffin chain, such as the products made
by reacting a long chaln para~in with sulfur dioxide and oxygen
under ultraviolet light, followed by neutralization with NaOH or
other suitable base. The paraffin sulfonates are the preferred
~ organic detergents of the invent~on and, without treatment by
the method of this invention, make the tackiest detergent
products. They are more particularly described below.
Other anionic surfactants are water soluble salts of,
for instance, s~uch high fatty carbo~ylic acids as lauric, myristic,
stearic-, oleic, elaidlc, isostearic, palmitic~ undecylenic,
tridecylenic, pentadecylenic3 2-lo~er alkyl hlgher alkanoic
(such as 2-methyl trldecanolc, 2-methyl pentadecanoic or 2-methyl
heptadecanoic) and other saturated or unsaturated fatty acids of
10 to 20 carbon atoms. Soaps of dlcarboxylic acids may also be
used, such as the soaps of dimerized linoleic acld. Soaps of
such other higher molecular weight acids such as rosin or tall
_ 8 -
~`6~3 ~ :~
oil acids, e.g., abietic acid, may also be employed.
Other anionic surfactants are sulfates o~ higher
alcohols~ such as sodium lauryl sul~a~e, sodium tallow alcohol
sulfate, sulfated oils, sulfates of mono- or diglycerides of
higher ~atty acids, e.g., stearic monoglyceride monosul~ate;
higher alkyl polyethenoxy ether sul~ates, i.e., the
sulfates of the condensation products o~ ethylene oxide and
a higher aliphatic alcohol, e.g., lauryl a~cohol, wherein the
molar proportion of alkylene oxide to alcohol is ~om 1:1 to
5:1; lauryl or other higher alkyl glyceryl ether sulfonates;
aromatlc polyethenoxy ether sulfates~ such as the sulfates of
the condensation products of Pthylene oxide and nonyl phenol
(usually having 1 to 20 oxyethylene groups per molecule,
preferably 2-12). The ether sulfate may also be one having a
lower alkoxy (of 1 to 14 carbon atoms, e.g., methoxy) sùbstltuent
- on a carbon close to that carrying the sul~ate group, such as a
monomethyl ether monosulfate of a long chain vicinal glycol,
e.g., a mixture of viclnal alkanediols o~ 16 to 17 or 18 or 20
carbon atoms in a straight chainO
Additional water soluble anionic sur~actants include
the higher acyl sarcosinates, e.g., sodium lauroyl sarcosinate;
the acyl esters, e.g., oleic acid ester o~ isethionates; and
acyl N-methyl taurides, e.g., potassium N-methyl lauroyl- or oleyl
tauride. Another type o~ anlonic sur~actant is a higher alkyl
~ .
_ g _ ' ~
106~
phenol sulfonate, for example, a higher alkyl phenol disulfonate.
The disul~onate may be one whose phenolic hydroxyl group is
blocked, as by etheri~ication or esterification; thus the H of
the phenollc OH may be replaced by an alkyl, e.g., ethyl, or
hydroxy polyalkoxyalkyl, and the resulting alcoholic OH may be
esterified to ~orm sulfate.
While the a~orementioned structural types of organic
carboxylates, sulfate, and sulfonates are generally preferred
types of anionic sur~actants, the correspondlng organic
phosphates and phosphonates are also use~ul.
Generally, the water soluble anionic organic surfactants
are ~lt8 0~ alkali metal cations, such as potassium, lithium,
and especlally sodlum although salts of ammonium cations and
substituted ammonium cations derived from lower (2 to 4 carbon
atom) alkanolamides, e.g., triethanolamine, tripropanolamlne, and
diethanol monopropanolamine, and from lower (l to 4 carbon atom)
alkyl amines, e.g., methylamine, ethylamine, 8ec - butylamine,
dimethylamine, tripropylamine and triisopropylamine, may be
utilized too.
The nonionic surfactants having the most desirable
detergency properties are usually lnherently unctuous pasty or
tacky solids at room temperature~ such as those having melting
points below about 40C. Typical nonionic detergents are
polyethenoxy derivatlves that are usually prepared by the
condensation of eth~lene oxide with compoùnds having a
- 10 --
6~7;~
.:.
hydrophobic hydrocarbon chain and containing one or more active
hydrogen atoms, such as higher alkylphenols, higher fa~ty alcohols,
higher fatty acids, higher fatty mercaptans, higher fatty amides
and polyols, e.g., fâtty alcohols having an 8 to 20, typically 10
to 18 carbon atom alkyl chain and alkoxylated with an average of
about 3 to 20, typically 5 to 15 alkylene oxide units. Commercial-
ly available nonionic suractants falling into this category are
Neodol* 45-11, which is an ethoxylation product ~having an average
of 11 ethylene oxide units) of a 14 to 15 carbon chain fatty
alcohol (Shell Chemical Company); Neodol 25-7, a 12 to 15 carbon
: ~
chain fatty alcohol ethoxylated with an average of 7 ethylene
oxide units; Alfonic* 1618-65, a 16 to 18 carbon alkanol ethoxylated
with an average of 10 to 11 ethylene oxide units ~Continental Oil
Company); and Pluronic* B-26, a 12 to 13 carbon alcohol etherified
with ethyl~e oxide and propylene oxide ~BASF ~hemical Company).
Cationic organic surfactants include quaternary amines ~ !
having a water soluble anion such as acetate, sulfate or
chloride. Suitable quaternary ammonium salts may be derived from
a higher fatty primary amine by condensation 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 ~`thylene oxide condensates
of N-tallow trimethylene dialnine (Armour Industrial Chemical Co.)
and Ethoquad* 18/12, 18/25 and 0/12, which are polyetho~rlated ~ -
c~uatema~y amm mium chlo ides (Armou~ Indumt~ial Chemical Co,~
'"''.
*Trademark
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Cationic surfactants also include quaternary ammonium salts -
de'rived from heterocyclic aromatic amines such as Emcol* E-607
which is N~lauryl colamino formyl methyl) pyridinium chloride
~Witco Chemical Corp.). Also sometimes classified as cationic
surfactants are higher fatty amine oxides such as Aromox* 18/12,
which is bis (2-hydroxyethyl) octadecylamine oxide ~Armour
Industrial Chemical Co.).
Amphoteric organic surfactants are generally higher ;
:,., :
fatty carboxylates, phosphates, sulfates or sulfonates which
contain a cationic substituent such as an amino group, which may -~
be quaternized, e.g., with a lower alkyl group, or chain extended
at the amino group by àondensation with a lower alkylene oxide,
e.g., ethylene oxide. In some instances the amino group may be
a member of a heterocyclic ring. Re~resentative commercial
water soluble amphoteric organic surfactants include Deripha ~151,
which is sodium ~-coco betaamine propionate ~General Mills, Inc.) ~:
and Miranol* C2M (anhydrous acid) which is the anhydrous form of
the heterocyclic diamino-dicarboxylate, sold by Miranol Chemical Co.
Preferably the normally tacky water soluble organic -
surfactant which is used to prepare the free flowing detergent
powder of the invention is an anionic surfactant and of these, ~.~
especially preferred are the higher paraffin sulfonates. The i-
hydrocarbon substituent of the par~ffin sulfonate preferably
contains 13 to 17 or 20 carbon atoms. The paraffin sulfonate
will normally be a monosulfonate but, if desired, may be a,!di-~;
*Trademark
-12-
- . : ,, :
tri- or higher sulfonate. Typically, a paraffin sulfonate may be employed
in admixture with the corresponding monosulfonate, for example, as a mix-
ture of mono- and di-sulfonates containing up to about 30% of the disulfo-
nate.
The hydrocarbon substituent of the paraffin sulfonate will usually
be linear but if desired branched chain paraffin sulfonates can be employed.
The paraffin sulfonate used may be terminally sulfonated or the sulfonate `
substituents may be joined to the 2-carbon or other carbon atom of the
paraffin chain. Similarly, any di- or higher sulfonate employed may have
the sulfonate groups distributed over different carbons of the hydrocarbon
chain.
The weight ratio of molecular sieve zeolite and normally tacky
organic surfactant employed to prepare the free flowing pulverulent deter-
gent compositions of the invention will be in the range of about 20:1 to
0.5:1, preferably being about 1:1 to 0.9:1. ;
The free flowing pulverulent detergent composition of the inven-
tion has an excellent detersive effect on most types of soils but, if desired
it may be combined with detergency adjuvants, such as builder salts, optical
brighteners, anti-redeposition agents and the like, which are conventional
ingredients in laundry detergents and other types of solid or particulate
washing agents. In such detergent formulations the proportion of zeolite-
organic surfactant composition is generally about 20 to 70% and preferably
is about 25 to 55% by weight. ;~
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The water insoluble molecular sieve zeolite present in the com-
positions of the invention has an excellent building effect on the deter-
gency of the composition. However, if desired, additional water soluble
builder salt or mixtures of such salts may be added. Representative organic
builder salts include the water soluble salts of nitrilotriacetatic acid,
citric acid, 2-hydroxyethylene iminodicarboxylic acid, boroglucoheptanoic
acid and polycarboxylic acids, e.g., polymaleates of low molecular weight
~generally below 1,000, e.g., ~00, 600 or 800~. Representative inorganic
builder salts include alkali metal silicates, e.g., sodium silicates, having
Na20:SiO2 molar ratios of 1:2 to 1:3.2, preferably 1:2 to 1:2.5, alkali
metal polyphosphates, such as pentasodium tripolyphosphate and tetrasodium
pyrophosphate; and alkali metal carbonates, such as sodium carbonate.
An especially desirable additional builder salt is sodium sili-
cate, which is particularly effective in sequestering magnesi~m cation, and
this is useful in overcoming magnesium hardness in the wash water. A pre-
ferred suitable laundry detergent formulation which contains a water soluble
anionic organic surfactant or detergent built with both molecular sieve zeo-
lite and sodium silicate is described in copending Canadian Patent Applica-
tion of B. Cheng, Serial No. 226,363, filed May 6, 1975, entitled "Detergent
Composition".
The amount of additional builder salt(s) charged to the zeolite- -
organic surfactant compositions of the invention
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may be from about 5 to 50% by weight of the final laundry
detergent formulation and preferably is from about 10 to 35%.
Similar proportions of inorganic filler salt, e.g., sodium
sulfate, so~ um chloride, may be employed.
The laundry~ldétergent formulations which are prepared
from the invented molecular sieve zeolite-organic surfactant
; compositions may also advantageously include small amounts, e.g.,
0.05 to 8%, of additional conventional detergent adjuvants, the
total amount of such minor adjuvants generally not exceeding
20%, preferably not exceedin~ 10% of the product. ;
These adjuvants include inorganic pigments, e.g.,
ultramarine blue; organic pigments, e.g., Indanthreane Blue* RS,
dyes, e.g., Color Index Direct Blue l; and especially the
fluorescent dyes known as optical brighteners. Such brighteners
may be coumarin, triazolyl stilbener~ stilbene cyanuric, `
acylamino stilbene or miscellaneous types shown in issued
; patents. The concentration of brightener is advantageously in
the range of about 1/20% to 1%, e.g., 1/10% to 1/2%.
The minor adjuvants may also include an organic gum
anti-redeposition agent, such as sodium carboxymethyl cellulose,
polyvinyl alcohol, hydroxymethyl ethyl cellulose, polyvinyl
pyrrolidone, polyacrylamide, hydroxypropyl ethyl cellulose or
,.
mixtures thereof. Preferably the anti-redeposition agent is
sodium carboxymethyl cellulose.
Additional minor detergent adjuvants which may be
included in the detergent formulation include perfumes;
,,
*Trademark
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, :,: . , . ,, ,'' ,` .. , , . ,.. ,, ' . :,
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i73
fun~icides or preservatives such as polyhalosalicylanilides, for
instance, tetrachlorosalicylanilide; sanitizersl such as
trichlorocarbanilide; foam suppressors, such as NrN-dilauryl
~or di-coco alcohol) amine; enzymes, such as the subtilisin
protease sold as Alcalase; bleaching agents, such as N-bromo
and N-chloro imido compounds, for example, di- and tri-chloro
(or bromo) cyanuric acid and water soluble salts thereof;
fabric softeners, such as l,2 alkane diols of 15 to 18 carbon
atoms; and flow improving agents, such as the clay product,
Satintone .
The detergent formulation may also contain a small
amount of moisture, in addition to that which may be adsorbed in
the zeolite molecular sieve, typically about 1 to S~.
The present compositions have been found to be effective
detergents against a wide variety of soils,including clay and
carbon soils, skin soil, natural and artificial sebum soils,
particulate soils, etc., on a wide variety of fabrics, including
cQtton, nylon and polyesters, such as polyethylene terephthalate
and various blends, e.g., cotton-polyester.
~he present compositions are highly effective detergents
even in the absence o conventional builder salts and other
detergent adjuvants due to the excellent detergency building
effect of the molecular sieve zeolite component. The molecular
sieve zeolite components are highly efficient in sequestering
calcium ion when washing in water of high calcium hardness.
Accordinglyj at a conventional laundry wash water concentration
of about 0.15%, the present compositions remain effective as
,
- 16
t73
detergents even at calcium ion concentrations of 150 p.p.m.
(as CaCO ) or higher. On washing of fabrics with the present
compositions no noticeable deposits of insolubles remain on the
fabrics after rinsing and tumble drying, even in the absence
of anti-redeposition agent in the formulation. It was surprising
to discover this exce~le~ r.on-deposition characteristic of the
present product in view of the known water insolubility of the
molecular sieve zeolite component of the mixture. When tumble
drying is not employed there may be a very slight deposit but
it is much less than would be expected. Also, the zeolite
molecular sieve is biologically safe, non-eutrophic, non-polluting
and is harmless to laundry and laundry equipment. Any white
fabrics washed with the present surfactant mixtures in the
presence of colored fabrics are not substantially stained by
dyes fugitive from the colored fabrics.
In addition to good building effects the present zeolite
molecular sieves also counteract tackiness of detergents to a
surprising extent, making them usefully free flowing and better
able to be compounded with other detergent composition ingredients.
They are superior in this respect to ordinary clays and
particulate carriers and they are useful builders, too.
The~following examples illustrate the invention but
do not limit it. Unless otherwise indicated, all parts are by
weight and temperatures are in C.
- 17 -
..~
73
EXAMPLE 1
~6 '
Paraffin sulfonate C15 (1~ 52.6
Molecular sieve zeolite 4A (2) 47.4
100.0
(1) A normally tacky sodium paraffin sulfonate wherein the
n-alkyl substituent contains on the average 15 carbon atoms
(Hoechst Chemical Corp.)
(2) A type 4A synthetic sodium molecular sieve ~eolite containing
2% moisture (proportions of molecular sieve zeolites given
in this and followiny examples are on an anhydrous basis)
having a mean particle diameter of 8.3 microns.
The paraffin sulfonate, which is a sticky, tacky,
intractable, semi-solid at ambient temperature, is charged to a
glass mixing vessel and the molecular sieve zeolite is added.
The vessel and its contents are agitated at ambient temperature
for 15 minutes by rotation on a roll mill. On completion of
; agitatlon there is obtained a ~cmogeneous mixture which contains
the molecular sieve zeolite and paraffin sulEonate in a ratio of
0.93:1 and whichis afree flowing non-tacky powder of excellent
detergent properties when used to wash laundry at about 0.15%
concentration in an automatic washing machine. The free Elowing
pulverulent zeolite-built surfactant retains its excellent~
homogeniety, flowability and non-tackiness,even on long storage
in non-barrier containers.
In a variation of the above example substantially
'' ' ' '. .
; - 18 - ~
, ,:
:. . .... . .
., . ,, . . . . ., . .: . , . . .: . . . . .. ....
6~,.6ti'3
similar excellent results are obtained when the molecular sieve
zeolite is replaced by a sodium molecular sieve zeolite of
crystalline type A having a mean particle diameter of 6.1 microns.
Similar excellent results are also obtained when the
paraffin sulfonate is replaced by a mixture of sodium n-alkane
monosulfonates of C14 and C15 chain lengths in approximately 2:1
ratio, said mixture also containing about 8~ of the corre~ponding
n-alkane disulfonates~ 3% of unreacted paraffin starting material,
and 5% of sodium sulfate.
.
EXAMPLE 2 ~
' % ~.
Molecular sieve z olite 4A (as in Example 1) 51
Higher fatty carboxylic acid soap (3) 49
100.0
(3) The water soluble sodium soap of ~0% tallow fatty acid
and 20~ coconut oil fatty acid.
The soap,which is a waxy solid at room temperature, of
poor flow properties as fine particles,is agitated with the
zeolite molecular sieve substantially as described in Example 1.
There is obtained a free ~lowing homogeneous powder in which the
weight ratio of zeolite molecular sieve to the organic surfactant
is about 0.95:1. The pulverulent product is non-sticky and has
good detergent characteristics, with the molecular sieve helplng
to build it.
. , :
'
- 19
6~3
EXAMPLE ~ % .
Molecular sieve zeolite 4A ~as in Example 1) 50 .
Neodol* 45-11, nonionic surfactant (4) 50
~4) A water soluble nonionic detergent which is the reaction
product of 11 mols of ethylene oxide and 1 mol of a mixture
of C14 and C15 straight chain primary alkanols, said mixture ..
averaging about 14,5 carbon atoms in the alkyl substituent
(Shell Chemical Co.) ;
The nonionic surfactant, which is a sticky, semi-solid
at room temperature, is agi-tated with the zeolite molecular sieve .
substantially as described in Example 1. There is obtained a
free flowing homogeneous powder in which the weight ratio of
the molecular sieve zeolite to the organic surfactant is about :;~
1:1. The pulverulent product is non-sticky and has good detergent
and 10w characteristics. Flow is improved further by increasing
the proportion of the molecular sieve, se~uentially to 2:1, 4:1, ;:
l0:1 and 80:1, with respect to the surfactant. ;
EXAMPLE ~ %
Molecular sieve zeolite, 4A (as in Example 1) 50
Miranol* C2M (anhydrous acid) (5) 50
(5) An amphoteric water soluble surfactant containing both
anionic and cationic substituents, as the anhydrous form of ,
the acid of the formula :
*Trademark ~:
-20- ~ . '
,.", ~, :
. ..
~ 3
C H 3 ¦~ ¦ / CH2CH20CH2CooH
11 2
~ CH2COOH
OH
(Miranol Chemical Co., Inc.)
The amphoteric surfactant, which is a tacky paste at '
,
room ~emperature, is mixed with the molecular sieve zeolite substan-
tially as described in Example 1. There is thus obtained a free
fIowing homogeneous powder in which the weight ratio of the
molecular sieve zeolite to the organic surfactant is about 1
The pulverulent product is non-tacky and has 'good detergent
characteristics. Flowability is not as good at a ratio of 0.5:1
but is better than for the surfactant particles above. At 10~
and 50:1 ratios flowability is much improved. Similar results r .
are obtained when half the Miranol* C2M is replaced by either the
paraffin sulfonate of Example 1 or the cationic compound, dimethyl ic~ ; ;
di-hydrogenated tallow ammonium chloride, and half the quantity of , -
molecular sieve is also replaced ~y a Type X or Y sieve. `; -
EXAMPLE 5 ~ ~
.... - .
.j . - .
Paraffin sulfonate C15 (as in Example 1) 10
Molecular sieve zeolite 4A (as in Example 1) 19.6
So~ium silicate (6) 15
NTA organic builder (7) 15
r : .
Neodol* 45-11 nonionic surfactant (as in Example 1) 2 ;~
~ i:;
CMC anti-redeposition agent (8) 0.5 ~
: . : ,' . : . .
Optical brightener (9) 0.3
Sodium sulfate filler 35.4
Water 2.2
100 .0
* Trademark -21
- :~
r--_
36~67;~
(6) Na2O:SiO2 = 1:2.35
(7) Trisodium nitrilotriacetate (added as the monohydrate but
proportions given are on an anhydrous basis)
(8) Sodium carboxymethyi cellulose (detergent grade)
S (9) 4,4'-bis(4-phenyl-2H-1,2,3-triazol-2-yl)-2,2'-stilbene
dïsulfonic acid, potassium salt.
The paraffin sulfonate and half of the molecular sieve
zeolite are agitated as described in Example 1 to obtain a free
flowing, non-tacky, pulverulent mixture. The remaining portion of
the molecular sieve zeolite and the nonionic surfactant are
agi~ated as described in Exa~ple 3.
The two mixtures are mixed in the dry state by agitation
in a ribbon mixer for about 5 minutes. To the resulting particulate
mixture. the silicate, organic builder salt, anti-redeposition
agent, optical brightener and filler salt are added. The agitation
of the resultant mass is continued for 8 minutes and the resultant
particulate solid laundry detergent is dropped from the mixer.
The detergent product is added to water of 150 p.p.m. CaCO3
equivalent mixed calcium and magnesium hardness (calcium ion:
magnesium ion ratio of 3:2) with about 1.5 grams of the detergent
composition being charged per liter of water. The aqueous
detergent is used to wash various fabrics in a conventional
automatic washing machine at a washing temperature of about 50C.,
with the period for agitated washing before spinning, i.e., before
centrifuging to remove the wash water prior to rinsing, being
,
- 22
\
. .
'73
about 10 minutes. In automatic washing tests the detergent
composition is highly effective as a detergent,washing out a wide
variety of 50ils including clay and carbon soils, skin soils,
natural and artificial sebum soils and particulate soils from a
variety of fabrics,including cotton, nylon and polyester, e.g.,
polyethylene terephthalate, and cotton-polyester blends. In
these washing experiments only a very slight, almost unnoticeable
insoluble residue is left on the clothes after rinsing, if they
are line dried and none is noted after tumble drying. Thls excel-
lent non-deposition characteristic of the detergent formulation
obtains even when the anti-redeposition agent (CMC) is omitted
from the detergent composition.
Fugutive dyes, which may bleed from colored fabrics
into the wash water and stain white or undyed fabrics when
conventional detergents are used, do not s~ain white fabrics when
tbe zeolite mol~cular sieve containing detergents of the invention
are employed to wash white and dyed clothes together.
In the foregoing detergent formulation and in the
previous examples, whereapplicable, it will be appreciated that
the silicate and/or the organic builder salt can be replaced
completely or in part by other builder salts, e.g., sodium
carbonate, 2-hydroxyethyl imino diacetic acid, disodium salt
and/or pentasodium tripolyphosphate. SimiIarIy the sodium
carboxymethyl cellulose can be replaced by other anti-redeposi-
tion agents,such as polyvinyl pyrrolidone and polyvinyl alcohol,
.
_ 23
\
~;.0~ 7~
and the filler salt can be replaced by another inert salt, such as
sodium chloride. The zeolite molecular sieve can be replaced by
other effective molecular sieve zeolites,including those of
types X, Y and L or mordenite, chabazite and erionite crystal
structures. Components and proportions may be varied,as described
in the oregoing specification and free flowing products are
obtainable. If desired, the formulations may be spray dried, spray
cooled or post sprayed, but direct "dry" mixing is usually prefer-
red because it saves energy, is less apt to cause pollution and is
easier to effect with equipment that requires lower capital
investments.
The invention has peen described with respect to working
examples and illustrations thereof but is not to be limited to
these because it is evident that one of skill in the art with
- 15 access to the present specification will be able to employ
substitutes and equivalents without departing from the spirit
or scope of the inventlon.
', . ...
_ 24
. \ .
~ .
