Note: Descriptions are shown in the official language in which they were submitted.
~15ZZ6~
FAERIC SOFTENING COMPOSITIONS
Maxie Davis, Jr.
Technical Field
This invention relates to solid com- -
positions and methods for conditioning fabrics in home
laundering operations. Compositions and methods are dis-
closed which provide for conditioning fabrics in through-
the-wash laundering operations as well as during the rinse
cycle of home laundering operations. It is a common prac-
n tice to impart to laundered fabrics a texture or handlethat is smooth, pliable and fluffy to the touch (i.e. soft)
and also to impart to the fabrics a reduced tendency to
pick up and/or retain an electrostatic charge (i.e. static
control), especially when the fabrics are dried in an
automatic dryer.
It has become commonplace today for homemakers
to use fabric conditioning compositions. A common practice
is to use fabric conditioning compositions for use in the
rinse cycle which comprise major amounts of water, lesser
amounts of fabric conditioning agents and minor amounts
of optional ingredients such as perfumes, colorants, pre-
servatives and stabilizers. Such compositions can be con-
veniently added to the rinsing bath of home laundry oper-
ations. An alternative method is to provide laundering
compositions containing the fabric conditioning agent which
deposits on the fabric and is carried through the wash and
rinse cycles to provide the fabric conditioning property
on the dried fabric.
Background Art
3C The use of organic cationic fabric softeners is
known. Blomfield in U.S. Patent 3,095,373 discloses
cationic chemical compounds having at least one hydrophobic
-
1~ 2 -
chain having at least 16 carbon atoms for use as softening
agents for laundered fabrics.
The use of clays as softening agents is also
known. A number of kinds of clay have been suggested for
5 use in detergent compositions for many years, for example,
British patents 401,413, Mariott, accepted Nov. 16, 1933 and
461,221, Marriott et al, accepted Feb. 12, 1937 disclose
the use of colloidal bentonite in synthetic detergent com-
positions, built or unbuilt, intended for the washing of
hair, textiles, or hard surfaces. More recently British
patent 1,400,898, Storm and Nirschl, sealed Nov. 19, 1975
disclosed the use of certain smectite clays in built deter-
gent compositions to provide through-the-wash fabric sof'ten-
ing, and British patent 1,401,726, Ohren, sealed Nov. 25,
1975 disclosed the use of those clays in soap compositions
containing a minor amount of synthetic'detergents as curd
dispersants. Other prior art references have disclosed
the use of clay in washing compositions to provide other
benefits, such as builder, water-softener, anticaking
agent, suspending agent, soil release agent,'hair ulling
agent, and filler.
The use of clay and organic cationic fabric
softening ingredient combinations in detergent compositions
for the simultaneous purpose of cleaning and softening
fabrics, in addition to other auxiliary benefits, such
as static control, is also known. Bernardino in U.S.
Patent 3,886,075 discloses compositions comprising par-
ticular smectite clays, cationic anti-static agents and
certain substituted amino compatibilizing agents which
are detergent compatible and provide softening and anti-
static benefits to fabrics washed therein. Speakman in
U.S. Patent 3,948,790 discloses detergent compositions
containing short chain quaternary ammonium clays which
are effective in providing fabric softening with non-
ionic detergents.
llSZ26Z
C. F. Battrell, U.S. Patent 4,292,035,
issued September 21, 1981 discloses that complexes of
clay and the organic fabric softening agent are useful
in softening clothes both in the rinse and through-the-
wash. Battrell teaches that the composition must
contain an anionic surfactant which is present in at
least 30% molar equivalence to the organic fabric
softening agent to provide wetting and dispersion of
the complex.
Disclosure of the Invention
The present invention relates to fa~ric condition-
ing compositions in solid form for use in the home launder-
ing process. These compositions comprise three essential
components: (a) from about 10% to about 80% by weight of an
impalpable smectite clay having an ion exchange capacity of
at least 50 meq/100 grams; (b) from about 1% to about 50% by
weight of said clay of a compound selected from the group
consisting of organic primary, secondary, and tertiary
amines,and their water soluble or water dispersible salts,
and organic ~uaternary ammonium,phosphonium,and sulfonium
compounds wherein said compounds have at least one hydro-
carbon group having from 8 to 22 carbon atoms; and (c) from
about 10% to about 90~ of an electrolyte having a solubility
in water of at least about 7 parts per 100 parts of water
at 20C.; wherein components (a~ and (b) are combined to
form a complex. It has been unexpectedly discovered that
the electrolyte provides sufficient wetting and dispersion
of the clay/organic softening agent without requiring the
inclusion of an anionic surfactant.
~ . ~
.
115Z26Z
-- 4 --
These novel compositions provide fabric softening
in the rinsing operation of typical laundering processes
or can be admixed or incorporated into granular or solid
detergent cleaning formulations to provide through-the-wash
5 fabric softening.
Detailed Description of the Invention
.
The Clay
The first of the three essential ingredients
of this invention is smectite clay. The clay is com-
plexed with the organic fabric softening agent to pro-
vide the fabric conditioning utility. Smectite clay
is present in the granular fabric conditioning compo-
sition at levels from about 10~ to about 80%, preferably
from about 20% to about 60%, by weight of the compo-
sition.
The clay minerals used to provide part of thesoftening properties of the instant compositions can
be described as impalpable, expandable, three-layer
clays, in which a sheet of aluminum/oxygen atoms or
magnesium/oxygen atoms lies between two layers of
silicon/oxygen atoms, i.e., alumino-silicates and mag-
nesium silicates, having an ion exchange capacity of
at least 50 meq./100 g. of clay. The term "impalpable"
as used to describe the clays employed herein means
that the individual clay particles are of such a size
that they cannot be perceived tactilely. Such particles
sizes are within the range below about 100 microns in
effective diameter. In general, the clays herein have
an ultimate particle size within the range from about
l micron to about 50 microns. The term "expandable"
` ` llSZZ6Z
-- 5 --
as used to describe clays relates to the ability of the
layered clay structure to be swollen, or e~panded, on
contact with water. The three-layer expandable clays
used herein are examples of the clay minerals classified
~geologically as smectites.
There are two distinct classes of smectite clays
that can be broadly differentiated on the basis of the
numbers of octahedral metal-oxygen arrangements in the
central layer for a gi~en num~er of silicon-oxygen
atoms in the outer layers. The dioctahedral minerals
are primarily trivalent metal ion-based clays and are
comprised of the prototype pyrophyllite and the members
montmorillonite (OH)4Si8_yAly(A14_xMgx) 20
(OH34Si8_yAly(A14_xFex)O20, and volchonskoite
lS (H)4si8_yAly(Al4-xcrx)o2ot where x has a value of from
0 to about 4.0 and y has a value of from 0 to about
2Ø Of these only montmorillonites having exchange
capacities greater than 50 meq/100 g. are suitable for
the present invention and provide fabric softening
benefits.
The trioctahedral minerals are primarily
divalent metal ion based and comprise the prototype
talc and the members hectorite (OH)4Si8 yAly(Mg6 XLix)O20,
saponite (oH)4(si8-yAly)(Mg6-xAlx)o2o~
(H)4Si8_yAIy(Zn6-xAlxlo2o~ vermiculite (OH)4Si8 Al
(Mg6_xFex)O20, wherein y has a value of 0 to about 2.0
and x has a value of 0 to about 6Ø Hectorite and
saponite are the only minerals in this class that are
of value in the present invention, the static reduction
or fabric softening performance being related to the
type of exchangeable cation as well as to the exchange
capacity.
The smectite clays useful in the present in-
vention are hydrophilic in nature, i.e. they display
swelling characteristics in aqueous media.
It is to be recognized that the range of the
water of hydration in the above formulas can vary with
the processing to which the clay has been subjected.
This is immaterial to the use of the smectite clays in
I
1~5ZZ6Z
the present invention in that the expandable character-
istics of the hydrated clays are dictated by the silicate
lattice structure.
As noted hereinabove, the clay minerals employed
in the compositions of the instant invention contain
cationic counterions such as protons, sodium ions,
potassium ions, calcium ions, magnesium ions, li'hium
ions, and the like. It is customary to distinguish
between clays on the basis of one cation predominantly
or exclusively absorbed. For example, a sodium clay
is one in which the absorbed cation is predominantly
sodium. Such absorbed cations can become involved in
exchange reactions with cations present in aqueous
solutions. A typical exchange reaction involving a
smectite clay is expressed by the following equation:
smectite clay (Na~ +NH40H ~ smectite clay (NH4) ~NaO~
Since in the foregoing equilibrium reaction, one equivalent
weight of ammonium ion replaces an equivalent ~eight of
sodium, it is customary to measure cation exchange ca-
pacity (sometimes termed "base exchange capacity") interms of milliequivalents per 100 g. of clay(meq./100 g.).
The cation exchange capacity of clays can be measured in
several ways, including by electrodialysis, by exchange
with ammonium ion followed by titration or by a methylene
blue procedure, all as fully set forth in Grimshaw,
"The Chemistry and Physics of Clays", pp. 264-265,
Interscience ~1971). The cation exchange capacity of a
clay mineral relates to such factors as the expandable
properties of the clay, the charge of the clay, which
in turn, is determined at least in part by the lattice
structure, and the like. The ion exchange capacity
of clays varies widely in the range from about 2 meq/
100 g. for kaolinites to about 150 meq/100 g., and
greater, for certain smectite clays. Illite clays
although having a three layer structure, are of a non-
expanding lattice type and have an ion exchange capacity
` ` ilSZZ6Z
-- 7
somewhere in the lower portion of the range, i.e., around
26 meq/100 g. for an average illite clay. Attapulgites,
another class of clay minerals, have a spicular (i.e.
needle-like) crystalline form with a low cation exchange
S capacity (25-30 meq/100 g.). Their structure is com-
posed of chains of silica tetrahedrous linked together
by octahedral groups of oxygens and hydroxyls containing
Al and Mg atoms.
It has been determined that illite, attapulgite,
and kaolinite clays, with their relatively low ion ex-
change capacities, are not useful in the instant compo-
sitions. However the alkali metal montmorillonites,
saponites, and hectorites and certain alkaline earth metal
varieties of these minerals such as calcium and sodium
montmorillonites have been found to show useful fabric
softening benefits when incorporated in compositions in
accordance with the present invention.
Specific non limiting examples of such fabric
softening smectite clay minerals are:
Sodium Montmorillonite
Brock ~
Volclay ~C
Gelwhite GP
Thixo-Jel~ 1
Ben-A-Gel~
.
Sodium Hectorite
Veegu ~
Laponite~SP
Sodium Saponite
Barasy ~ AS 100
Calcium Montmorillonite
Soft Clar
Gelwhite~L
115Z262
-- 8 --
Lithium Hectorite
~a
Barasym~IH 200
Most of the smectite clays useful in the com-
positions herein are commercially available under various
trademarks, for example, Thixo-Jel #1 and Gelwhite GP
from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay
BC and Volcaly #325, from ~merican Colloid Co., Skokie,
Illinois; and Veegum F, from R. T. Vanderbilt. It is
to be recognized that such smectite minerals obtained
under the foregoing tradenames can comprise mixtures of
the various discrete mineral entities. Such mixtures
of the smectite minerals are suitable for use herein.
Within the classes of montmorillonite, hecto-
rite, and saponite clay minerals having a cation e~-
change capacity of at least about 50 meq/100 g., certainclays are preferred for fabric softening purposes. For
example, Gelwhite GP is an extremely white form of
smectite clay and is therefore preferred when formulating
white or lightly colored agglomerates. Volclay BC which
is a smectite clay mineral containing at least 3~ of iron
(expressed as Fe2O3) in the crystal lattice, and which
has a very high ion exchange capacity, is one of the most
efficient and effective clays for use in agglomerated
fabric conditioning compositions and is preferred from
the standpoint of product performance. On the other
hand, certain smectite clays marketed under the name
"bentonite" are sufficiently contaminated by other
silicate minerals, as evidenced by a low colloid content
(~50~) that their ion exchange capacity falls helow the
requisite range, and such clays are of no use in the
instant compositions.
Bentonite, in fact, is a rock type originating
from volcanic ash and contains montmorillonite (one
of the smectite clays) as its principal clay component.
The Table shows that materials commercially available under
the name bentonite can have a wide range of cation
llSZ2f~Z
e.Ychange capacities and fabric softening performance.
Mixtures of two or more types of clay are con-
templated within the scope of this invention.
EXCHANGE CAPACITY
5 BENTONITE meq/100 q. _FTENING ABILITY
Brock 1 63 Good
Soft Clark 84 Good
Bentolite L 1 68 Fair - Good
Clarolite T-60 61 Fair
10 Granulare 2
Naturale Bianco 23 Fair - Poor
Thixo-Jel #4 55 Poor*
Granular
Naturale Normale 19 Poor
15 Clarsol FB 5 3 12 Poor
PDL 1740 26 None
Versuchs 4
Product FFI 26 None
SUPPLIED BY AND TRADEMARK OF:
1 Georgia Kaolin Co. USA
2 Seven C. Milan Italy
3 Ceca Paris France
4 Sud-Chemie Munich Germany
* Low colloid content ( ~50~)
2S It has also been found that certain smectite
minerals can reduce or eliminate the buildup of static
electricity on fabrics washed in the compositions. The
visible evidence that static buildup has been prevented
is the absence of "cling", i.e., the tendency of dif-
ferent areas of fabric to adhere to one another. A
r
:,
`~ ~152262
-- 10 --
measure of the approach to static charge elimination is
the mean voltage of the fabric.
The smectite minerals that have proved to be
beneficial in reducing static buildup when incorporated
into agglomerated fabric conditioning compositions are
the lithium and magnesium hectorites and saponites, i.e.,
minerals of the structure (OH~4Si8 yAl (Mg6 Li )20
and (H)4si8_yAlyMg6-xAlxo2o respectively in which the
counter ions are predominantly magnesium or lithium, i.e.,
at least 50% of the counter ions are Li or Mg , the
remainder being other alkaline earth or alkali metal
counter ions.
Preferred minerals are those in which 75-90~
of the counter ions are lithium or magnesium and for which
the cation exchange capacities are greater than 60 meq/
100 g. Specific examples of such preferred materials
are magnesium hectorite, lithium hectorite, and magnesium
saponite.
It is believed that the universal henefit given
by the Mg+~ and Li~ hectorite and saponite clay minerals
is related to the size to charge ratio of these cations
and the unusually large nu~ber of moles of water that
can be held by them.
Minerals that have fabric softening character-
istics such as the sodium and calcium montmorillonitesand the sodium hectorites and saponites do not exhibit
appreciable antistatic activity, nor does magnesium
montmorillonite.
Accordingly, smectite clays useful in the fabric
conditioning compositions of this invention can be
characterized as montmorillonite, hectorite, and saponite
clay minerals having an ion exchange capacity of at least
about 50 meq/100 g. and preferably at least 60 meq/100 g.
Appropriate clay minerals for use herein can be
selected by virtue of the fact that smectites e~hibit a
true 14A x-ray diffraction pattern. This character-
istic pattern, taken in combination with exchange capacity
measurements performed in the manner noted above, pro-
vides a basis for selecting particular smectite minerals
for use in the granular fabric conditioning compositions
disclosed herein.
The smectite clays described hereinabove
function as fabric conditioning agents by depositing on
fiber surfaces, particularly cotton surfaces that are
negatively charged. They are effective, not only on the
surfaces of 100% cotton fabric, but also upon fabric blends
that contain significant amounts of cotton, for example
a 50% cotton/50% polyester blend. The discrete, in-
dividual smectite clay particles are in the form of flat
platelets, having a predominantly positive charge around
the edges where the crystal lattices are incomplete, and
having a predominantly negative charge on the flat sides
thereof.
The Organic Fabric Softening Aqent
The second essential ingredient of this in-
vention is the organic fabric softening agent which is
reacted with the clay to form the water insoluble complex.
The organic fabric softening agent is present in compositions
of this invention at levels of from 1~ to 53% by weight
of the clay component. Preferred levels range from 3%
to 30%, most preferred 5% to 20%, of the clay component.
In general, useful softeners are organic com-
pounds which contain primary, secondary, tertiary or
quaternary nitrogen or which are phosphonium or sul-
fonium compounds and have at least one relatively longhydrocarbon group substituent conferring hydrophobicity
and lubricity. Mixtures of these compounds can also be used
in this invention. Typical fabric softeners include
A. Primary, secondary,and tertiary amines and their
water soluble or water dispersible salts,and quaternary
ammonium compounds~ The general formulas for this group
are
l~SZZ62
- 12 -
lR2R3 ; ~ 1 2 3 4 ~n
wherein Rl represents an alkyl or alkenyl having from
about 8 to about 22, prefera~ly 12 to 18, carbon atoms and
R2, R3 and R4 each independently represent hydrogen or alkyl,
alkenyl, arylalkyl or alkylaryl having from 1 to 22 carbon
atoms, and X represents a water soluble or water dispersible
anion and n is an integer from 1 to 3, preferably 1 to 2.
Examples of suitable anions include hydroxide, chloride,
bromide, sulfate, methosulfate or similar anion.
Examples of the above include primary tallow amine,
primary tallow amine hydrochloride, primary coconut amine,
secondar~ tallow methyl amine, tallow dimethyl amine, coconut
dibutyl amine, monostearyl dimethyl ammonium chloride, tri-
oleyl ammonium chloride, dicoconut dimethyl ammonium chloride,
tallow trimethyl ammonium chloride, ditallow dimethyl
ammonium chloride, tetralauryl ammonium chloride, tetra-
tallow ammonium chloride, ditallow methyl ammonium chloride
and tallow dimethyl ammonium chloride. Preferred for use
in this invention are secondary ditallow amine, trilauryl
amine, tritallow amine, secondary dicoconut amine. A highly
preferred compound is ditallow methyl amine.
` .
B. The diamine and diammonium salts having the general
formulas
RlR~NR5NR3R4 ; [RlR2NR5NR3R4 6]n
1 2 3 5 4 6]n X ; [RlR2R3NR5NR4R6R7]2+ X2-
wherein Rl, R2, R3, R4, n and X are as defined above, R~
and R7 have the same definition as R2 to R4 and R5 is an
alkylene chain having from 4 to 6 carbon atoms wherein the
middle carbon atoms may be lin];ed to each other by an ether
30 oxygen or by a doul)le or triple hond. Common among the
available diamines are N-al~yltrimetllylene diamines
(R-I~EI-C3H6-NII2). ~ s~ecific example of a suitable diamine
is 2~2~-biststearyl dimethyl ammonio) diethylether
dichloride.
-- 115ZZ62
- 13 -
C. The ethoxylated amine and diamine salts with fatty
alkyl groups of coconut, tallow, soya and stearyl having
from 2 to 50 moles of ethylene oxide, typically with
2, 5, 15 or 50 moles ethylene oxide, are also suitable.
D. Alkyl imidazoline and imidazole salts wherein the
alkyl group is lauryl, oleyl, stearyl, or tall oil, are
also suitable for the invention provided the system is not
too alkaline. Specific examples of these compounds are
l-beta hydroxyethyl-2-stearyl imidazoline ammonium chlo-
ride and 2-stearyl-1, l-methyl [(2-stearylamido) ethyl]
-imidazolinium methosulfate.
E. Yet another suitable softening agent includes alkyl
pyridine and piperidine salts wherein the alkyl group has
from abcut 8 to 22 carbon atoms. Examples include stear-
amidomethyl pyridinium chloride, and stearyl pyridiniumchloride.
F. Yet other additional softening agents include alkyl
sulfonium and alkyl phosphonium salts wherein the alkyl
group has from 8 to 22 carbon atoms. Compounds in this
group are quaternized and will combine with the clay.
An example of a salt of this type is
~6~3~ ~ ~ ~ C~ Cl-
C2H5
G. Further additional softening agents include esters of
amino acids and amino alcohols wherein at least one of the
two hydrocarbon chains has from 8 to 22 carbon atoms and
the second hydrocarbon chain can be an alkyl having from
1 to 4 carbon atoms or an alkyl having from 8 to 22 carbon
atoms.
` -- 1152262
- 14 -
H. Further additional softening agents include the fatty
acid ester salts of mono-, di- ~nd tri-ethanolamine salts,
and the alkyl guanidine salts in which the alkyl group
contain 8 to 22 carbon atoms.
The suitable organic fabric softening agents
will combine with the clay to form a complex including
the compounds that are not in salt form.
The reaction of the organic cationic softener
with the $mectite clay proceeds predominantly via an
10 ion exchange mechanism until the cation exchange capacity
of the clay is approached and thereafter the mechanism is
one of adsorption~ The once negativel~ charged clay
particles become increasingly~ electropositive and with
continued adsorption a reversal of charges occurs for
15 the organo-clay complex. The interactions between the
clay and the organic cationic softener are strong and
change the physical properties of the clay (i.e.
viscosity, colloid stability, and the clay becomes
hydrophobic~.
; 20 ~ Conversely, the reaction of the neutral organic
softeners ~ith the smectite clay proceeds predominantly
via an adsorption mechanism. However, some ion exchange
between the softener and labile inorganic cations of the
clay has been observed. The interactions between the
25 neutral organic softener and the clay are strong and
change the physical properties of the clay in the same
way as was mentioned above for the organic cationic softener-
clay complexes.
1~2262
-- 15 --
The Electrolyte
The third essential ingredient of this invention is
the electrolyte which is the wetting and dispersing agent
for the complex. The electrolytes suitable for this in-
vention have a solubility of at least 7 parts, preferablyat least 10 parts, electrolyte per 100 parts of water at
20C. The electrolyte is present at levels of from about
10% to about 90%, preferably from about 20% to about 80~,
and most preferably from about 30% to about 50%, by weight
of the composition.
The electrolytes can be crystalline or amorphous
in nature. Further, they can be in either an anhydrous or
a hydrated form since either form is suitable for this in-
vention. The electrolytes promote rapid admission of
15 water into the solid compositions of this invention, rapid
dispersion of the composition into its ultimate particles,
and rapid dispersion of the ultimate particles of clay
throughout the rinsing bath.
When compositions of this invention are made by
20 agglomeration of the clay/organic fabric softening agent
complex and the electrolyte, the discrete individual
; particles of electrolyte before agglomeration have an
effective diameter below about 200 microns, and preferably
from about 30 to about 100 microns.
Preferred electrolytes are aluminum sulfate
and chloride and alkali metal and alkaline earth metal
chlorides, sulfates, carbonates, bicarbonates, sesqui-
carbonates, orthophosphates, pyrophosphates, tripoly-
phosphates, borates, silicates, nitrates, acetates,
30 urea and mixtures thereof that meet the solubility test
described hereinbeore. Sodium sesquicarbonate is a
highly preferred electrolyte for use in this invention.
; Other highly preferred electrolytes are hardness-
electrolyte salts, specifically salts of Ca and Mg
- 115Z262
Especially highl~ preferred are magnesium sulfate, magnesium
chloride, and calcium chloride. These hardness-electrolyte
salts still further and unexpectedly increase the fabric
conditioning effectiveness of the instant compositions.
S While not wishing to be bound by theory, it is believed
that there are two phenomena at work which effect the
beneficial results of hardness-electrolytes on fabric
conditioning. One factor appears to be that, the negative
charges on fabric surfaces and the negative charges present
10 on the faces of the smectite clay platelets are bridged
by the hardness-electrolyte thereby increasing the at-
traction of the clay/organic fabric softening agent complex
to the fabric surfaces, and hence increase their deposition.
The second factor is that the hardness-electrolyte will
15 destabilize the organic softening agent-clay complex disnersion
by collapsing the double layer repulsion forces between
the clay platelets allowing the complex to deposit more
readily on the fabric surfaces.
It ~ill be appreciated that hardness-electrolyte
20 salts are especially beneficial when the ~ater used for
the rinsing bath is soft, i.e., contains hardness below about
3 grains per U.S. gallon expressed as CaCO3. Increased
effectiveness in fabric conditioning, relative to soft
water, was noted for compositions of the instant invention
25 wherein the water hardness of the rinse bath was 15 grains
per U.S. gallon.
Non-limiting examples of the solubility of
electrolyte materials are (parts electrolyte per 1~
parts water at 20C.): aluminium sulate octadecahydrate
30 (36), calcium chloride hexahyclrate (74), magnesium chloride
hexahydrate (54), magnesium sulfate heptahydrate (35),
sodium carbonate decahydrate (21), sodium sulfate heptahydrate
(19), sodium chloride (101), anhydrous sodium carbonate (15),
anhydrous sodium bicarbonate (9), sodium sesquicarbonate (19).
` llsæ6z
- 17 -
Optional Ingredients
Anionic Surfactants
The softener composition need only include the
organo-clay complex and the eIectrolyte. The composition
5 can also include a minor amount of an anionic surfactant.
When included, the anionic surfactant is present at from
about 1~ to about 29% molar equivalence to the organic
softening agent. Preferably the anionic surfactant is
present at a level of from about 5~ to about 25~, most
10 preferably from about 10% to about 20~, molar equivalence
to the organic fabric softening agent.
Water-soluble salts of the higher fatty acids,
i.e., "soaps" are useful as the anionic surfactant herein.
This class of surfactants includes ordinary alkali metal
15 soaps such as the sodium, potassium, ammonium, and
alkanolammonium salts of higher fatty acids containing
from about 8 to about 24 carbon atoms and preferably
from about 10 to about 20 carbon atoms. Soaps can be made
by direct saponification of fats and oils or by neu-
20 tralization of free fatty acids. Particularly usefulare the sodium and potassium salts of the mixtures of
fatty acids, derived from coconut oil and tallow, i.e.,
sodium or potassium tallow and coconut soaps.
The anionic synthetic surfactants suitable for
25 this invention include water-soluble salts, particularly
the alkali metal salts, or organic sulfuric reaction
products having in their molecular structur~ an alkyl
group containing from about 8 to about 22 carbon atoms
and a moiety selected from the group consisting of
30 sulfonic acid and sulfuric acid ester moieties. (Included
` 115Z262
- 18 -
in the term alkyl is the alkyl portion of higher acyl
moieties.) Examples of this group of synthetic surfact-
ants which form a part of the softener compositions of
the present invention are the sodium and potassium alkyl
sulfates, especially those obtained by sulfating the higher
alcohols (C8-C18 carbon atoms~ produced by reducing the
glycerides of the tallow or coconut oil; sodium and po-
tassium alkyl benzene or toluene sulfonates in which
the alkyl group contains from about 9 to about 20,
9 to 15 preferred, carbon atoms in straight chains or
branched-chain configuration, e~g. those of the type
described in United States Patents Number 2,220,099
and 2,477,383 (especially Yaluable are linear straight
chain alkyl benzene sulfonates in which the average of
the alkyl groups is about 11.8 carbon atoms and com-
monly abbreviated as Cll 8LAS); sodium alkyl glyceryl
ether sulfonates, especially those ethers of higher
alcohols derived from tallow and coconut oil; sodium
coconut oil fatty acid monoglyceride sulfonates and
sulfates; sodium and potassium salts of sulfuric acid
esters of the reaction product of one mole of a higher
fatty alcohol (.e.g. tallow or coconut oil alcohols)
and about 1 to 6 moles of ethylene oxide; sodium and
potassium salts of alkyl phenol ethylene oxide ether
sulfates with about L to about 10 units of ethylene o~ide
per molecule and in which the alkyl groups contain from
about 8 to about 12 carbon atoms.
Anionic phosphate surfactants are also useful
in the present invention. These are surace active
materials in which the anionic solubilizing group
connecting hydrophoblc moieties is an o~y acid of
phosphorus. The more common solubilizing groups, of
' course are -SO4H and -SO3H. Alkyl phosphate esters
i such as (R-0)2PO2H and ROPO3H2 in which R represents
an alkyl chain containing from about 8 to about 20
carbon atoms are useful herein.
ilS2Z62
- 19 -
These phosphate esters can be modified by in-
cluding in the molecule from one to about 40 alkylene
oxide units, e.g., ehtylene oxide units. Formulae for
these modified phosphate anionic surfactants are
o
If
[ ( 2 2 ) ]2 or
[R-o-(cH2cH2o~n]-p-o-M
O-M
in which R represents an alkyl group containing from
about 8 to 20 carbon atoms , or an alkylphenyl group in
whieh the alkyl group contains from about 8 to about 20
earbon atoms, and M represents a soluble cation such as
hydrogen, sodium, potassium, ammonium or substituted
ammonium; and in which n is an integer from 1 to about
40.
Another class of suitable anionic organie sur-
factants particularly useful in this invention includessalts of 2-ae~loxy-alkane-1-sulfonic acids. These salts
have the formula
1OCIR2
Rl - CH - CH2S03M
where Rl i5 alkyl of about 9 to about 23 carbon atoms
(forming with the two carbon atoms an alkane group);
R2 is alkyl of 1 to about 8 carbon atoms; and M is a
water-soluble cation.
The water-soluble cation, M, in the herein-
before described structural formula can be, for e~ample,
115~262
- 20 -
an alkali metal cation (e.g., sodium, potassium, lithium),
ammonium or substituted-ammonium eation. Specific ex-
amples of substituted ammonium cations include methyl-,
dimethyl-, and trimethyl- ammonium cations and quaternary
a~monium eations such as tetramethyl-ammonium and dimethyl
piperidinium eations and those derived from alkylamines
such as ethylamine, diethylamine, triethylamine, mixtures
thereof, and the like.
Speeifie examples of beta-aeyloxy-alkane-l-
sulfonates, or alternatively 2-aeyloxy-alkanel-1-sul-
fonates, useful herein include the sodium salt of 2-
aeetoxy-tridecane-l-sulfonie aeid; the potassium salt of
2-propionyloxy-tetradeeane-1-sulfonie aeid; the lithium
salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the
sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonie aeid;
the sodium salt of 2-aeetoxy-hexadecane-1-sulfonie acid;
the potassium salt of 2-oetanoyloxy-tetradecane-1-sulfonie
aeid; the sod~um salt of 2-acetoxy-heptadeeane-1-sulfonie
aeid; the lithium salt of 2-acetoxy-oetadeeane-1-sulfonie
aeid; the potassium salt of 2-acetoxy-nonadecane-1-
sulfonic aeid; the sodium salt of 2-acetoxy-uneosane-1-
sulfonie aeid; the sodium salt of 2-propionyloxy-docosane-
l-sulfonie acid; the isomers thereof.
Examples of beta-aeyloxy-alkane-l-sulfonate salts
herein are the alkali salts of beta-acetoxy-alkane-
l-sulfonie aeids corresponding to the above formula wherein
Rl is an alkyl of about 12 to about 16 earbon atoms.
Typical examples of the above deseribed beta-
aeetoxy alkanesulfonates are deseribed in the literature:
Belgium Patent 650,323 issued July 9, 1963, diseloses
the preparation of eertain 2-aeylo~y alkanesulfonie aeids.
Similarly, U.S. Patents 2,094,451 lssuecl September 28,
1937, to Guenther et al. and 2,086,215 issued July 6,
1937,to DeGroote disclose certain salts of beta-acetoxy
alkanesulfonie aeids.
~ li5ZZ62
- 21 -
Another preferred class of anionic surfactant
compounds herein is the alkylated C~-sul~ocarboxylates,
containing about 10 to about 23 carhon atoms, and having
the formula
o
l~
R - CH - C - OR'
so3
wherein R is C8 to C20 alkyl, M is a water-soluble
cation as hereinbefore disclosed, preferably sodium
ion, and R' is short-chain alkyl, e.g., methyl, ethyl,
propyl, and butyl. These compounds are prepared by
the esterification of ~ -sulfonated carboxylic acids,
which are commercially available, using standard
techni~ues. Specific examples of the alkylated ~-
sulfocarboxylates preferred for use herein include:
ammonium methyl- ~-sulfopalmitate,
triethanolammonium ethyl- d-sulfostearate,
sodium methyl- d-sulfopalmitate,
sodium ethyl- ~-sulfopalmitate,
sodium butyl- ~-sulfostearate,
potassium methyl- ~-sulfolaurate,
lithium methyl- ~-sulfolaurate,
i as well as mixtures thereof.
Another class of anionic organic surfactants
is the ~ - alkyloxy alkane sulfonates. These compounds
have the following formula:
l~2 ll
Rl - C - f SO3M
H H
where Rl is a straight chain alkyl group having from
6 to 20 carbon atoms, R2 is a lower alkyl group having
from 1 (preferred) to 3 carbon atoms, and M is a water-
soluble cation as hereinbefore described.
llSZZ6Z
- 22 -
Specific examples of ~ -alkyloxyl alkane sul-
fonates, or alternatively 2-alkyloxy-alkane-1-sulfonates,
having low hardness (calcium ion) sensitivity useful herein
to provide superior cleaning levels under househola
washing conditions include:
potassium-~-methoxydecanesulfonate,
sodium 2-methoxytridecanesulfonate,
potassium 2-ethoxytetradecylsulfonate,
sodium 2-isopropoxyhexadecylsulfonate,
Iithium 2-t-butoxytetradecylsulfonate,
sodium ~ -methoxyoctadecylsulfonate, and
ammonium ~ -n-propoxydodecylsulfonate,
Other synthetic anionic surfactants useful herein
are alkyl ether sulfates. These materials have the formula
RO(C2H4O)XSO3~ wherein R is alkyl or alkenyl of about 10
to about 20 carbon atoms, x is 1 to 30, and M is a water-
soluble cation as defined hereinbefore. The alkyl ether
sulfates useful in the present invention are condensation
products of ethylene oxide and monohydric alcohols having
about 10 to about 20 carbon atoms. Preferably, R has 14
to 18 carbon atoms. The alcohols can be derived from
~fats, e.g., coconut oil or tallow, or can be synthetic.
Lauryl alcohol and straight chain alcohols derived from
tallow are preferred herein. Such alcohols are reacted
with 1 to 30, and especially 6, molar proportions of
ethylene oxide and the resulting mixture of molecular
species, having, for example, an average of 6 moles of
ethylene oxide per mole of alcohol, is sulfated and
neutralized.
Specific examples of alkyl ether sulfates of the
present invention are sodium coconut alkyl ethylene
glycol ether sulfate, lithium tallow alkyl triethylene
glycol ether sulfate; and sodium tallow alkyl he~aoxy-
ethylene sulfate.
Preferred alkyl ether sulfates (commonly ab-
breviated as AEXS) are the alkali metal coconut- and
~152Z6;2
- 23 -
tallo~-alkyl oxyethylene ether sulfates having an average
of about 1 to about 10 oxyethylene moieties. The alkyl
ether sulfates of the present invention are known compounds
and are described in U.S. Pa~ent 3,332,876, to Walker
(July 25, 1967)
~dditional examples of anionic non~SaP synthe-
tic surfactants which come within the terms of the present
invention are the reaction product of fatty acids
esterified with isethionic acid and neutralized with
sodium hydroxide where, for example, the fatty acids are
derived from coconut oil; sodium or potassium salts of
fatty acid amides of methyl tauride in which the fatty
acids, for example, are derived from coconut oil.
Other anionic synthetic detergents of this variety are
set forth in United States Patents 2,486,921; 2,486,922;
and 2,3~6,278.
Additional examples of anionic, non-soap,
synthetic surfactants, which come withi.n the terms of
the present invention, are the compounds which contain
two anionic functional groups. These are referred to as
di-anionic detergents. Suitable di-anionic surfactants
are the disulfonates, disulfates, or mixtures thereof
of which may be represented by the following formulae:
R(SO3)2M2, R(SO4)2M2, R(SO3)(SO4)M2,
where R is an acyclic aliphatic hydrocarbyl group having
15 to 20 carbon atoms and M is a water-solubilizing cation,
for e.xample, the C15 to C20 disc)dium 1,2 alkyldisulfates,
C15 to C20 dipotassium-l, 2-alkyldisulfonates or disulfates,
disodium 1,9-he~adecyl disulfates, C15 to C20 disodium-
1,2-alkyldisulfonates, disodium l,9-stearyldisulfates and
6,10-octadecyldisulfates.
The aliphatic portion of the disulfates or
disulfonates is generally substantially linear, thereby
26Z
imparting desirable biodegradable properties to the
surfactant compound.
The ~ater-solubilizing cations include the
customary cations known in the detergent art, i.e., the
alkali metals, and the ammonium cations, as well as
other metals in group IIA, IIB, IIIA, IVA and IVB of
the Periodic Table except for boron. The preferred water-
solubilizing cations are sodium or potassium. These
dianionic surfactants are more fully described in ~ritish
10 Letters Patent 1,151,392 which claims priority on an
application made in the United States of America (No.
564,556) on July 12, 1966.
Still other anionic synthetic surfactants in-
clude the class designated as succinamates and succinates.
This class includes such surface active agents as
disodium N-octadecylsulfo-succinamate; tetrasodium N-
(1,2-dicarboxyethyl)-N-octadecylsulfo-succinamate; diamyl
ester of sodium sulfosuccinic acid; dihexyl ester of
sodium sulfosuccinic acid; dioctyl esters of sodium sul-
fosuccinic acid.
Other suitable anionic surfactants utilizableherein are olefin sulfonates having about 12 to about 24
carbon atoms.
The c~-olefins from which the olefin sulfonates
are derived are mono-olefins having 12 to 24 carbon atoms,
preferably 14 to 16 carbon atoms. Preferably, they are
straight chain olefins. Examples of suitable l-olefins
include l-dodecene; l-tetradecene; l-hexadecene; 1-
octadecene; l-eicosene and l-tetracosene.
In addition to the true alkene sulfonates and
a proportion of hydro~y~alkanesulfonates, the olefin sul-
fonates can contain minor amounts of other materials,
such as alkene disulfonates depending upon the reaction
conditions, proportion of reactants, the nature of the
starting olefins and impurities in the olefin stoc~ and
side reactions during the sulfonation process.
~52262
- 25 -
A specific anionic surfactant which has also
been found excellent for use in the present invention is
described more fully in the U.S. Patent 3,332,880 of
Phillip F. Pflaumer and Adrian Kessler, issued July 25,
1967, titled "Detergent Composition".
Of all the above-described types of anionic
surfactants, preferred compounds include sodium linear
alkyl benzene sulfonate wherein the alkyl chain averages
from about 10 to 18, more preferably about 12, carbon
atoms in length, sodium tallow alkyl sulfate; 2-acetexy-
tridecane-l-sulfonic acid; sodium methyl- ~-sulfopalmitate;
sodium ~ -methoxyoctadecylsulfonate; sodium coconut alkyl
ethylene glycol ether sulfonate; the sodium salt of
the sulfuric acid ester of the reaction product of one
mole of tallo~ alcohol and three moles of ethylene oxide;
and mixtures thereof.
Additional Optional Ingredients
Additional optional ingredients include from 0.01
to about 2%, preferred 0.02% to 1% of sodium toluene sul-
fonate and/or sodium xylene sulfonate as processing aidsfor the anionic surfactant.
Additional optional ingredients include minor
amounts, of from 0.01% to about 1% to colorant, perfume,
fabric brighteners, photoacti.ve bleaching a~ent such as
sulfonated zinc phthalocyanine, and the li~e.
Processing
The softener composition is made by combining
the three essential ingredients in two basic mcthods.
In one method, agglomeration, the first step
in the process is to contact the smectite clay with the
', ~
il52Z62
- 26 -
organic softener to form the organo-clay complex. This
step is conveniently carried out in an aqueous system.
The complçx will form at ambient temperatures especially
if the organic softener is in the salt form. If the
5 organic softener is not in the salt form and is a solid
then the softener should be melted before addition to
the clay to conveniently form the complex. Temperatures
up to about 80C. can conveniently be employed in making
the organo-clay complex.
In the second step the organo-clay complex is
aqqlomerated with the electrolyte by spraying onto the organo-
clay complex and electrolyte mixture a binding/matrixing
agent (e.g. water, electrolyte solution, anionic sur-
factant, etc.).
When the second method, slurry-drying, is
to be employed, the first step in making the composition
is to make a slurry of the electrolyte in water, add
the clay and then finally add the organic softener to
complex the clay with the organic softener. This slurry
20 is then converted into a solid form by driving off
the excess moisture.
Non-limiting examples of the equipment available
for agglomeration include a cement mixer, Dravo pan ag-
glomerator, KG/Schugi Blender-Granulator whirling knife
2S continuous vertical fluidized bed agglomerator, Niro
Fluidized Bed and Obrian Mixed/Agglomerator.
Non-limiting examples of equipment available
for the slurry-drying method include a spray drying
tower, prilling tower, roll dryer and extr-lsion processes.
In the process of making the sof~ener compositions
the optional ingredients can serve as processing aids.
The particle size of the granules, whether made
by agglomeration or by slurry-drying will vary. The
preferred size for use of the fabric softener compositions
35 of this invention in the granular form is from about 20
; mesh to about 65 mesh (Tyler).
llSZ26Z
- 27 -
As disclosed herein the softener composition
comprising the three essential ingredients is intended
for use in providing softening for fabrics during the
rinsing operation which follows washing. Alternatively
the fabric softener compositions can simply be admixed
with a detergent composition or added to a washing
solution to provide fabric softening through the wash.
EXAMPLE I
Test towels consisting of 100% cotton were
10 washed in an upright machine using a regular granular
detergent under thé following conditions:
Product concentration : 0.25% (127.5 g in 13.5 gal.
water)
Product composition : 20% surfactant (70/30 C12
branched alkyl benzene
sulfonate/C12 branched
toluene sulfonate), 33%
STPP, 10% silicate solids
(2SiO2/Na20), 25% Na2SO4,
2~ sodium toluene sulfonate,
balance water and miscel-
laneous.
Water hardness : 19 gr/gal, 3/1 Ca/Mg ratio
Water temperature : 70~75F.
25 Water:Cloth ratio : 20 to 1
Towels of 86% cotton/14% polyester were
included with the test towels to make up
a full wash load
Washing time : 20 minutes
...
After washing, the towels were hand wrung and
agitated in the washer for 5 minutes in 13.5 gallons of
70~F, 9 grain hardness 3/1 Ca/~lg ratio water to rinse
. `` ~lSZZ6Z
- 28 -
Following the first rinse the fabrics were
again hand wrung and agitated as in the first rinse except
that the second rinse Water included the fabric softening
compositions as indicated below. The fabrics were then
wrung and line dried following which the test fabrics were
graded for softness in a round robin panel test. Three
judges were employed in the grading using a 0 to 4 grading
scale wherein the scale has the following meaning: 0 - no
difference; 1 - guess that there is a difference; 2 - small
difference; 3 - moderate difference; 4 - large difference.
The compositions tested and the results after two wash-
rinse cycles are given below~
Softener Composit-ion No. No. 1No. 2 No. 3
Complex of
Clay - Ca montmoEillonite 45.0%40.0% 30.0%
Primary tallow amine
hydrochloride ----- ---- 5.0
Tertiary ditallow methyl ~ ¦
amine 5.0 5.0 ----
Branched C12 alkyl-
benzene sulfonate,
Na salt ---- 9.09 9.09
Sodium toluenesulfonate ---- 0.91 0.91
Sodium carbonate -- - ----- 5.0
25 Sodium sulfate ---- 9.1 6.4
Sodium bicarbonate ~ --- 4.6
Sodium sesquicarbonate
(anhyd. basis) ,' 39.4 25.2 28.2
Color/Perume 0.150.15 0.6
30 Water 10.0 10.0 10.0
Miscellaneous Bal. Bal. Bal.
Amount of product in
2nd rinse - g. 50 50 50
Concentration o~ product 0.1% 0.1~ 0.1%
~l~Z;262
- 29 -
Softness Results
Blank No. 1 No. 2 No. 3
~o softener in
the 2nd rinse)
5 Softness
panel score
(averaged
results)O(STD~ ~2.3 +2.3 +1.5
Least significant difference = 0.5 at 95% confidence
All three softening compositions were made by
spray drying.
As shown by the results all three compositions were
effective in softening cotton towels. Composition 1, which
is within the scope of this invention, was as effective in
15 fabric softening as Were compositions 2 and 3 which included
a surfactant for dispersion of the complex.
EXAMPLE II
The compositions shown in Example I were tested
for their dispersability in Water.
The procedure consisted of adding 500 ml. of
tap water (7Q-75F., 9 grains/gallon hardness) to a glass
quart jar. The water ~as stirred ~ith a 2 inch magnetic
stirrer sufficient to produce about 1-1/2 inch vortex.
Then 1.25 grams of product was added to the vortex and
the time re~uired for product to disperse was recorded.
The indication that the product dispersed was shown by
the water becoming cloudy with inability to see the vortex
in a side view of the glass jar.
Composi-tion Dispersion Time
30 No. 1 from Ex. I 10-12 seconds
No. 2 from Ex. I 5-6 seconds
No. 3 from Ex. I 5-6 seconds
All three compositions dispersed well in this
test including Composition No. 1 which is within the
scope of this invention.
^` 1~52262
- 30 -
EX~MPLE III
Test towels consisting of 100% cotton were washed
in a bench-scale laboratory washing machine using a
regular granular detergent under the following conditions:
Product concentration ; 0.25~(9.45 g in l.0 gal.
water)
Product composition : 20% surfactant (70/30 C12
branched alkyl benzene
sulfonate/C12 ~ranched
toluene sulfonate), 33~
STPP, 10% silicate solids
(2SiO2/Na20), 25~ Na2SO4
2~ sodium toluene sulfonate,
balance water and miscel-
laneous.
Water hardness : 19 gr/gal, 3/1 Ca/Mg ratio
Water temperature : 70-75F.
Water: Cloth ratio : 20 to 1
~ashing time : 20 minutes
After ~ash~ng, the towels were hand wrung and
agitated in the washer for 5 minutes in 1.0 gallon of
70F., 9 grain hardness 3~1 Ca/Mg ratio water to rinse.
Following the first rinse the fabrics were
again hand wrung and agitated as in the first rinse except
that the second rinse water included the fabric softening
compositions as indicated below. The fabrics were then
wrung and line dried followlng which the test fabrics
~ere graded for softness in a round robin panel test as
in Example I.
The compositions tested and the results obtained
after one wash-rinse cycle are given below.
1152Z62
~ - 31 -
Composition No. 4 5 6
Complex of
Clay-Ca montorillonite 45.0 ~ 45.0 % 45.0 %
Primary tallow amine ---- 5.0 5.0
Ditallow methyl amine 5.0 ---- ----
Branched C 2 alkylbenzene
sulfonate, Na salt 0.91 ---- 1.48
Sodium toluenesulfonate 0.09 ---- 0.15
Sodium Carbonate 19.7 ---- 18.9
Sodium bicarbonate 17.9 ____ 17.2
Sodium sesquicarbonate
(anhyd basis) ---- 39.4 -----
Sodium sulfate 0.7 ---- 1.4
Colorant/perfume 0.65 0.15 0.65
Water 10.0 10.0 10.0
Miscellaneous Bal. Bal. Bal.
~Molar equivalence of
surfactant to amine 29 % 0 % 25 %
Prod. conc. in 2nd rinse 0.1 % 0.1% 0.1%
Softness Results
Blank No. 4 No. 5 No. 6
(No softener in
the second rinse)
Softness paneT1 sc~ore
(a~Teraged results) O(STD) +2.8+1.1 +1.9
Least significient difference = 0.7 at 95S confidence.
~ ` 115Z262
- 32 -
The results show that all three compositions,
which are all within the scope of this invention, softened
the test towels. Composition No. 5 was not as effective
in fa~ric softening as the other two compositions. Composition
No. 6 which has the same clay-organic softener complex as
No. 5 but additionally contains a minor amount of surfactant
shows improved softening performance relative to No. 5.
~15;22~i2
- 33 -
EX~IPLE IV
The following fabric softening compositions are
prepared in accordance with the invention.
ComPosition No. 7 8 9 10 11 12 13
5 Comp~ex of
Clay
Na hectorite 10 25
Na montmoril-
lonite 70 15 50
Na saponite 40 40
Sec. Dicoconut
amine 3 20
Dicoconut
methyl amine 5
Sec dital~o~ 5
Dicoconut di-
methyl am-
monium chlo-
ride 6.0
I Tallow tri-
j~ methyl am-
!: monium chlo-
ride 5
Ditallo~ di-
~ methyl am-
I monium chlo-
! ride 10
Na C12 0.54.0 0.3 1.0 1.0
Na C14-16 alkyl
E S 0.5 0.3
Na toluene sul-
fonate 0.05 0.3 0.03 0.1 0.1
Na sesquicar-
bonate (anhyd.
basis~ 72.0 10.030.0 65~0 57.0 40.0 37.0
Na sulfate 0.05 0.3 0.03 0.1 0.
~ r^7ater + minors
', (perfume,
~ 40 colorant etc.) 15.012.9 S 4 14.34 lI. a ~_,
k
SZ26Z
- 34 -
The above compositions can be used in the rinsing
operation in the home laundering process to provide
fabric softening.
Alternatively the above compositions can be
5 added to the washing solution to provide fabric softening
through the wash provided the washing solution contains a
predominant amount of anionic surfactant relative to other
surfactants.
EXAMPLE V
The following fabric softener compositions are
prepared in accordance with the in~ention.
Composition No. 14 15 16
.
Complex of
Brock clay 50 50 50
Palmityl methyl
ëthyl sulfonium
chloride 5
Monostearyl tri-
l~ methyl phosphonium
,~ 20 chloride 5
I l-beta hydoxyethyl-
; 2-stearyl imidazo-
line 5
12 1.0 1.0 1.0
25 Na toluene sulfonate 0.1 0.1 0.1
Na sesquicarbonate
(anhyd. basis) 36.0 36.0 36.0
Water ~ minors
(perfume colorant
etc.) 7.9 7.9 7.9
