Note: Descriptions are shown in the official language in which they were submitted.
~2~3~
This invention relates to detcrgent compositions and
in particular to detergent-softe]ler compositions capable of
imparting improved softness, detersive effects 9 soil anti-
redeposition and antistatic properties -to fabrics treated
therewith and particularly in a machine laundering p-rocess.
The detergent compositions of this invention are also outstanding
in that they result in less greasy staining (due to the catiollic
softener) of the laundered and dried clothes.
Compositions for simultaneously achieving detergency
and an appreciable level of softness in the machine laundering
of fabrics, and thus suitable for use in the wash cycle~ are
well-known and widely available commercially. The fugitive
interaction between anionic surfactant, perhaps the most commonly
used of the available types of surfactants, and cationic softeners
particularly those of the di-lower-di-higher alkyl qua~ernary
ammonium type, is likewise well recognized in the patent literature.
Such interaction often results in the formation of unsightly pre-
cipitates which become entrapped within or otherwise deposited upon
the fabric being washed. Discoloration or other aesthetical
displeasing effects are for the most part inevitable. The net
result is often a depletion in the effective amount of anionic
available for useful purposes since the loss of anionic is the
primary consequence.
Remedial techniques heretofore proposed to abate the
aforedescribed cationic-anionic problem though divergent as to
approach seem convergent as to result namely, less than satisfactory.
~Z23~
Thus, although the most effective types of cationic quaternary
ammonlum softeners, as exemplifiecl by the aforementioned di-
higher alkyl type quats, such as clistearyl dimethyl ammonium
chloride, can function in the wash cycle in the presence of
anionic, builder, etc., the quantity needed to achieve effective
softening is usually coterminous with amounts promotive of
undesired cationic-anionic interaction. As a general rule, at
least about twice as much cationic is required fo~ sof-tening as
for antistat.
In U.S. 3,325,4]4, dealing primarily with detergents
of controlled foam or sudsing capability, the cationic-anionic
problem and attendant detrimental effects are discusedd in
detail. The patent additionally points out that certain quater-
nary ammonium compounds, amoung the class of cationic agents, are
generally unstable when heated and when in contact with alkaline
builders, the instability being manifested by the development
of strong amine odors and undesirable color. The compositions of
the patent are limited to the use of quaternary ammonium halides
having but one higher alkyl group, the given structural formula
for the cationic being correspondinglv limitedO Cationics of
this type are markedly inferior to the di-higher alkyl types at
least insofar as fabric softening activity is concerned.
Other prior art teachings at least tactically avoid the
use of cationic softeners altogether proposing the use of, for
example, anionic materials as softening agents. U.S. 3,~7~,338
is representative, this patent teaching the use of anionic
softener referred to as "branched-chain carboxylic acids," as
fabric softener. Presumably, anionic detergent would be stable
in the presence of the anionic softener.
~ZZ34~i
As the foregoing demonstrates, the remedies proposed
necessitate the discarding of softeners and principally those of
the di-higher-di~lower a1kyl quaternary ammonium salt and cyclic
imide types, these having been determined by experience to be
among the most effective softeners thus far developed in the
art.
The problem of cationic incompatibility in anionic
detergents is also acknowledged in U.S. Patents 3,936,537 and
4,141,841 and it is therein proposed to employ as an essential
ingredient in combination with the cationic substance an organic
dispersion inhibitor. An important characteristic of such
inhibitors is a maximum water solubility at 25C of 50ppM.
Similar disclosures may also be found U.S. Patents 4,113,630;
4,196,104 and 4,272,385. In U.S. Patent No. 4,230,590 to Wixon
heavy duty detergents comprising conventional builder, princi-
pally anionic surfactant components, cationic softener and a
mixture of fatty acid soap and cellulose ether are disclosed.
The soap-cellulose ether mixture is in the form of a spaghetti,
flake or other shape and is present in the composition as
substantially homogeneously dispersed, discrete particles.
In U.S. Patent No. 4,298,480 to Wixon heavy duty
detergents having compositions similar to that described in the
preceeding paragraph with the exception that cellulose ether
is excluded therefrom are disclosed.
In U.S. Patent 4,329,237 to Wixon having duty deter-
gents also similar to those in the preceeding two paragraphs
are described except that the particles of soap are in admixture
with nonionic surfactant.
Although the above mentioned soap and cationic softener
containing detergent compositions possess desirable softening and
detersive properties, it has been found that optimum softening
without spot staining may not be attained.
-- 4
,
3~15
The present invention provides stable detergent softener composi-
tions capable of providing improved softness without stainillg, detergency,
antistatic and s~il antiredeposition properties to fabrics treated ~herewith
therewith in a laundering process in cold or hot water.
According to the present invention, there is provided a particu-
late detergent softener composition capable of imparting improved softness,
detergency, antistatic and nonstain properties to fabrics treated therewith
in a laundering process comprising by weight from about 5 to 40% of water
soluble non-soap, organic surfactant, from about 10 to 60% of water-soluble,
neutral to alkaline builder salt, from about 2 to 20% of cationic amine
softener-nonionic mixture, and from about 0 to 20% of water-soluble or dis-
persible fatty acid soap or a mixture thereof with nonionic organic surfac-
tant, the nonionic constitu~ing from about 2 to about 50% by weight of the
said soap mixture,wherein the ca~ionic-nonionic mixtureis substantially
homogeneously dispersed in said composition as discrete particles.
In another aspect, the invention provides a process for preparing
the composition hereinbefore defined which comprises spray drying the non-
soap organic surfactant and builder salt and to the spray-dried material
post adding the balance of ingredients.
The invention also provides a spray cooled softener composition
comprising an intimate blend of a cationic amine softener and from 2 to 20%
based on the weight of said mixture of a water-soluble non-ionic ethoxylate
surfactant active compound.
The compositions generally comprise by weight from about 5 to 40%
of a water-soluble, non-soap, anionic surfactant, fromabout 10 to 60% of water
soluble, neutral ~o alkaline builder salt, from about 2 to 20% of cationic
softener selected rom (a) aliphatic, di-(lower) Cl - C4 alkyl, di-(higher)
C14 - C24 a]kyl quaternary ammonium saltsJ (b) heterocyclic compounds, and
mixtures of (a) and (b), said cationic in intimate admixture with a water-
soluble nonionic (2 to 50% by weight based on weight of cationic), and from
about 0 to 20% of a mixture of water soluble or dispersible fatty acid soap
and nonionic organic surfactant in spaghetti-like or other shaped, discrete
-- 5 --
3~5
form, the weight ratio of soap (when used) to softener being from about 2:3
to 3:2, the per-cent concentration of anionic surfactant being at least about
].5 x + 5, x representing the per-cent concentration of softener, wherein
the soap is substantially homogeneously dispersed throughout said composition
preferably as discrete particles.
In the soap-nonionic surfactant mixture, the nonionic constitutes
from about 2 to about 50%, preferably from about 5 to about 40%, more pre-
ferably from about 8 to about 30%, and most preferably from about 8 to about
20%, all percentages being by weight. The totalnonionic surfactant content
in the soap mixture will vary from about 0.04% to about 10%, preferably from
about 0.1% to about 8%, and more preferably from about 1.6 to about 6%, and
most preferably from about 1.6% to about 4%, all percentages being by weight
and based on the weight of the detergent composition.
In certain other aspects~ the invention includes using the afore-
described compositions.
According to the present invention by adding the cationic material
in intimate admixture with nonionic organic surfactant in flakes, granules
and the like form, the spot staining of the clothes after drying is substan-
tially mitigated. In addition, the softness in the fabrics laundered is
generally unexpectedly enhanced. The nonionic surfactan~ also contributes
to soil antiredeposition, especially in non-phosphate formulas.
The inclusion of the nonionic organic surfactant in the cationic
softener composition has the following additional advantages. Typically,
nonionic surfactants are post-added to spray-dried detergent compositions.
As a result, the post-added nonionic surfactant increases the tackiness of the
detergent product. In the present invention, the nonionic surfactant is
included in the post-added cationic whichleads to a significant improvement
in the flowability of the detergent composition.
~2~34~
In the embodiments of the present invention utiliziny
soap particles with or without cellulose ether or non-ionic
surfactant as taught in the above-described Wixon patents the
useful fatty acids include generally those derived from natural
or synthetic fatty acids having from 10 to 30 carbons in the
alkyl chain. Preferred are the alkali metalsr e.g., sodium
and/or potassium soaps of C10 - C24 saturated fatty acids, a
particularly preferred class being the sodium and/or potassium
salts of fatty acid mixtures derived from coconut oil and tallow,
e.g., the combination of sodium coconut soap and potassium
tallow soap in the mutual proportions respectively of 15/85.
As is known as the molecular weight of the fatty acid is
increased, the more pronounced becomes its foam inhibiting
capacity. Thus, fatty acid selection herein can be made
having reference to the foam level desired with the product
composition. In general, effective results obtain wherein at
least about 50~ of the fatty acid soap is of the C10 - C18
variety. Other fatty acid soaps useful herein include those
derived from oils of palm groundnut, hardened fish, e.g., cod
liver and shark, seal, perilla, linseed, candlenut, hempseed,
wainut, poppyseed, sunflower, maize, rapeseed, mustardseed,
apricot kernel, almond, castor and olive, etc. Other fatty
acid soaps include those derived from the following acids:
oleic, linoleic, palmitoleic, palmitic, linoleic, ricinoleic,
capric, myristic and the like, other useful combinations
thereof including, without necessary limitation, 80/20 capric-
lauric, 80/20 capric-myristic, 50/50 oleic-capric, 90/10
capric-palmitic and the like.
The nonionic surfactants useful in the soap particles
and in admixture with the cationic are known materials. Such
nonionic surfactants may be broadly defined as water-soluble
compounds produced by the condensation of alkylene oxide groups
(hydrophilic in nature) with an organic hydrophobic compound,
which may be aliphatic or alkyl aromatic in nature. The length
of the hydrophilic or polyoxyalkylene radical which is condensed
with any particular hydrophobic group can be readily adjusted
to yield a water-soluble compound having the desired degree of
balance between hydrophilic and hydrophobic elements.
For example, a well known class of nonionic organic
surfactants is made available on the market under the trade mark
of "Pluronic". These compounds are formed by condensing ethylene
oxide with a hydrophobic base formed by the condensation of
propylene oxide with propylene glycol. The hydrophobic portion
of the molecule which, of course, exhibits water insolubility,
has a molecular weight of from about 1,500 to 1,800. The
addition of polyoxyethylene radicals to this hydrophobic portion
tends to increase the water solubility of 'he molecule as a
whole and the li~uid character of the product is retained up
to the point where polyoxyethylene content is about 50 percent
of the total weight of the condensation product.
Other suitable nonionic synthetic surfactants include:
1. The polyethylene oxide condensates of alkyl phenols,
e.g., the condensation products of alkyl phenols having an alkyl
group containing from about six to 12 carbon atoms in either a
straight chain or branched chain configuration, with ethylene
oxide, the said ethylene oxide being present in amounts equal
to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
The alkyl substituent in such compounds may be derived from
polymerized propylene, diisobutylene, octene, or nonene, for
example.
~2~34~;
2. Those derived from the condensation of ethylene
oxide with the product resulting from the reaction of propylene
oxide and ethylene diamine. For example, compounds containing
from about 40 percent to about 80 percent polyoxyethylene by
weight and having a molecular weight of from about 5,000 to about
11,000 resulting from the reaction of ethylene oxide groups with
a hydrophobic base constituted of the reaction product of ethyl-
ene diamine and excess propylene oxide, said base having a
molecular weight of the order of 2/500 to 3,000 are satisfactory.
3. The condensation product of aliphatic alcohols having
from 8 to 30 carbon atoms, in either straight chain or branched
chain configuration, with from 2 to 100 moles of ethylene oxide
e.g., a coconut alcohol-ethylene oxide condensate having from 5
to 30 moles of ethylene oxide per mole of coconut alcohol, the
coconut alcohol fraction having from 10 to 14 carbon atoms.
Nonionic surfactants include nonyl phenol condensed
with either about 10 or about 30 moles of ethylene oxide per
mole of phenol and the condensation products of coconut alcohol
with an average of either about 5.5 or about 15 moles of
ethylene oxide per mole of alcohol and the condensation product
of about 15 moles of ethylene oxide with one mole of tridecanol.
Other examples include dodecylphenol condensed with 12
moles of ethylene oxide per mole of phenol; dinonylphenol con-
densed with 15 moles of ethylene oxide per mole of phenol~
dodecyl mercaptan condensed with 10 moles of ethylene oxide per
mole of mercaptan; bis-(N-2-hydroxyethyl) lauramide; nonyl
phenol condensed with 20 moles of ethylene oxide per mole of
nonyl phenol; myristyl alcohol condensed with 10 moles of ethyl-
ene oxide per mole of myristyl alcohol; lauramide condensed with
15 moles of ethylene oxide per mole of lauramide; and di-iso-
_ g
~ 223~
octylphenol condensed with 15 moles of ethylene oxide.
Among the above-listed nonionic surfactants, the condens-
ation product of aliphatic alcohols having from 8 to 22 carbon
atoms with ethylene oxide is preferred. Typical examples of
such nonionic surfactants are Neodol* 25-7, a product of Shell
Chemical Co., which comprises the condensation pr~duct of
C12 15 alcohol with 7 moles of ethylene oxide, and Neodol*23-6.5
which is the product of a C12 13 alcohol with 6.5 moles of ethyl-
ene oxide.
Cationic softeners useful herein are known materials and
are of the high-softening type. Included are the N,N-di-(higher)
C14 - C24, N,N-di(lower) Cl - C4 alkyl quaternary ammonium salts
with water solubilizing anions such as halide, e.g., chloride,
bromide and iodide;sulfate, methosulfate and the like and
the heterocyclic imides such as the imidazolinium salts.
For convenience, the aliphatic quaternary ammonium salts
may be structurally defined as follows:
R - ~ X
wherein R and Rl represent alkyl of 14 to 24 and preferably 14
to 22 carbon atoms; R2 and R3 represent lower alkyl of 1 to 4
and preferably 1 to 3 carbon atoms, X represents an anion
capable of imparting water solubility or dispersibility includ-
ing the aforementioned chloride, bromide, iodide, sulfate and
methosulfate. Particularly preferred species of aliphatic
* Trade Marks 10
~L2;~34~S
quats include:
di-hydrogenated tallow dimethyl ammonium chloride
di-tallow dimethyl ammoni.um chloride
distearyl dimethyl ammonium methyl sulfate
di-hydrogenated talllow dimethyl ammonium methyl sulfate
Heterocyclic imide softeners of the imidazolinium type
may also, for convenience, be structurally defined as follows:
N- CH2
N ~ !H
R4 CH2C~2NH -C X
wherein R4 is lower alkyl of 1 to 4 and preferably 1 to 3
carbons; R5 and R6 are each substantially linear higher alkyl
groups of about 13 to 23 and preferably 13 to 19 carbons and
X has the afore-defined significance. Particularly preferred
species of imidazoliniums include:
methyl-l-tallow amido ethyl-2-tallow imidazolinium
methyl sulfate; available commercially from
Sherex Chemical Co. under the trade mark
Varisoft 475 as a liquid, 75% active ingredient
in isopropanol solvent,
methyl-l-oleyl amido ethyl-2-oleyl imidazolinium
methyl sulfate; available commercially from
Sherex Chemical Co. under the trade mark
Varisoft 3690, 75& active ingredient in
isopropanol solvent.
-- 11 --
3~
It is preferred ln one aspect of the present invention
where the soap and nonionic surfactant are used in combination
that the soap be used with at most equal and preferably minor
quantity of nonionic surfactant, e.g., from about 2% to about
50~ of the mixture preferably from about 5% to about 40%, more
preferably from about 8 to about 30%, and most preferably from
about 8 to about 20%, based on the total soap-nonionic surfac-
tant admixture for incorporation into the final detergent
composition, usually by post blending of both soap and the
cationic-nonionic mixture with dried detergent. The soap and
nonionic surfactant when combined may be first mixed in the
desired amounts to form a substantially homogeneous mass which
can be worked, according to well known technique, until it is
sufficiently "doughy" or plastic to be in suitable form for,
preferably, extrusion or other process, e.g., pelleting, gran-
ulation, stamping and pressing. Working may be effected, for
example, by roll milling, although this is not essential, fol-
lowed by extrusion in a conventional soap plodder with the
desired type of extrusion head. The latter is selected in
accordance with the shape, i.e., geometric form, desired in the
extrudate. Extrusion in the form of spaghetti or noodles is
particularly preferred. Other shaped forms such as flakes,
tablets, pellets, ribbons, threads and the like are suitable
alternatives. Special extruders for the foregoing purposes
are well known in the art and include for example Elanco*
models EXD-60; EXCD-100; EX-130 and EXD-180, a Buhler* extruder
and the like. Generally, the spaghetti extrudate is a form-
retaining mass, i.e., semi-solid and essentially non-tacky at
room temperature requiring in most cases no further treatment
such as water removal. If necessary, the latter can be effected
by simple drying techniques. The spaghetti should have an
* Trade Marks - 12 -
~L~3~S
average length of from about 2 to 20 mm. with about 95-- thereof
within a tolerance of 005 to 20 mm. and an average diameter or
width of from about 0.2 to 2.0 mm. with a range of 0.4 to 0~8
mm. being preferred. The bulk density of the spa~hetti will
usually, having reference to the type of fatty acid soap and
nonionic surfactant used, be from about 0.9 to 1.3 g/cm3.
Flakes will measure about 4 mm. in length and breadth and 6.2
mm. in thickness, pellets have a cross section of 2.5 mm. while
tablets have a cross section of 2.5 mm. and thickness of 2.5 mm.
The cationic-nonionic mixture may be prepared similarly
as for the soap-nonionic mixture. It is preferred however to
use the mixture in prilled form. The prills are produced by
spray cooling a liquefied mixture of the cationic and the non
ionic. In the most preferred embodiment a liquid non-ionic
is used (e.g., Neodol*23-6.5) and this is added to melted
cationic. A typical cationic is Arosurf*TA-100 (dimethyl
distearyl ammonium chloride) and as supplied this material forms
a very fluid liquid when melted and heated to 90C. The liquid
mixture of cationic and nonionic may in another preferred
embodiment may be allowed to cool to room temperature or as
necessary to solidify. The solid may then be ground to desired
particle size and post added to the other detergent ingredients.
Generally, from 1 to 20% be weight of non-ionic based
on the weight of the cationic softener is contemplated.
Preferably the nonionic should be used in amounts of from 5 to
15% with about 10% being particularly preferred in the case
of Neodol 23-6.5.
Although surfactants of conventional type can be used
herein, it is preferred that at least about 90% and preferably
at least about 95% of the total surfactant or detergent be of
the anionic type, these materials being particularly beneficial
* Trade Marks - 13 -
~3~
in heavy duty detergent for fabric washing. Anionics for use
herein generally include the water soluble salts of organic
reaction products having in their molecular structure an anionic
solubilizing group such as S04~1, S03H, COOH and P04H and an
alkyl or alkyl group having about 8 to 22 carbon in the alkyl
group or moiety. Suitable detergents are anionic detergent
salts having alkyl substituents of 8 to 22 carbon atoms such
as: water soluble sulfated and sulfonated anionic alkali metal
and alkaline earth metal and detergent salts containing a
hydrophobic higher alkyl moiety, such as salts of higher alkyl
mono- or poly--nuclear aryl sulfonates having from about 8 to 18
carbon atoms in the alkyl group which may have a straight
preferred or branched chain structure, preferred species
including, without necessary limitation: sodium linear tridecyl-
benzene sulfonate, sodium linear dodecyl benzene sulfonate,
sodium linear decyl benzene sulfonate, lithium or potassium
pentapropylene benzene sulfonate; alkali metal salts of sulfated
condensation products of ethylene oxide, e.g., containing 3 to
20 and preferably 3 to 10 moles of ethylene oxide, with aliphati~
alcohols containing 8 to 18 carbon atoms or with alkyl phenols
having alkyl groups containing 6 to 18 carbon atoms e.g., sodium
nonyl phenol pentaethoxamer sulfate and sodium lauryl alcohol
triethoxamer sulfate; alkali metal salts of saturated alcohols
containing from about 8 to 18 carbon atoms, e.g., sodium lauryl
sulfate and sodium stearyl sulfate; alkali metal salts of higher
fatty acid esters of low molecular weight alkylol sulfonic acid,
e.g., fatty acid esters of the sodium salt of isethionic acid;
fatty ethanolamide sulfates; fatty acid amides of amino alkyl
sulfonic acids, e.g., lauric acid amide of taruine; alkali metal
salts of hydroxy alkane sulfonic acids having 8 to 18 carbon
atoms in the alkyl group, e.g., hexadecyl, alphahydroxy sodium
sulfonate. The anionic or mixture thereof is used in the form
- 14 -
~l.Z23~
oi their alkali or alkaline earth metal salts. The anionic is
preferably of the non-soap type, it being preferred that the
soap component be utilized as taught herein. However, minor
amounts of soap, e.g., up to about 35% and preferably 20% based
on total anionlc can be added, for example, to the crutcher mix.
The concentration of non-soap anionic should preferably be
selected so as to provide an excess with respect to cationic-
softener according to the empirical relationship
% concentration - 1.5X + 5
wherein X is the per cent concentration of cationic softener.
This assures the minimum excess of anionic necessary for optimum
overall detergency, softening, etc. performance in the product
composition.
Minor amounts of other types of detergents can be
included along with the anionic, their sum in any case not
exceeding about 10% and preferably about 2-5% of total detergent,
i.e., such other detergent plus non-soap anionic. Useful here
are the nonionic surface active agents which contain an organic
hydrophobic group and a hydrophilic group which is a reaction
product of a solubilizing group such as carboxylate, hydroxyl,
amido or amino with ethylene oxide or with the polyhydration
product thereof, polyethylene glycol. Included are the condens-
ation products of C8 to C30 fatty alcohols such as tridecyl
alcohol with 3 to 100 moles ethylene oxide; C16 to Cl~ alcohol
with 11 to 50 moles ethylene oxide; ethylene oxide adducts with
monoesters of polyhydric alcohols, e.g., hexahydric alcohol;
condensation products of polypropylene glycol with 3 to 100 moles
ethylene oxide; the condensation products of alkyl ~C6 to C20
straight or branched chain) phenols with 3 to 100 moles ethylene
oxide and the like.
Suitable amphoteric detergents generally include those
containing both an anionic group and a cationic group and a
- 15 -
~23a~05
hydrophobic organic group which is preferably a higher aliphatic
radical of 10 to 20 carbon atoms; examples include the N-long
chain alkyl aminocarboxylic acids and the N-long chain alkyl
iminodicarboxylic acids such as described in U.S. 3,824,189.
The compositions herein preferably include water solu~le
alkaline to neutral builder salt in amounts of from about 10 to
60% by weight of total composition. Useful herein are the
organic and inorganic builders including the alkali metal and
alkaline earth metal phosphates, particularly the condensed
phosphates such as the pyrophosphates or tripolyphosphates,
silicates, borates, carbonates, bicarbonates and the like.
Species thereof include sodium tripolyphosphate, trisodium phos-
phate, tetrasodium pyrophosphate, sodium acid pyrophosphate,
sodium monobasic phosphate, sodium dibasic phosphate, sodium
hexametaphosphate; alkali metal silicates such as sodium
metasilicate, sodium silicates: Na2O/SiO2 of 1.6:1 to 3.2:1,
sodium carbonate, sodium sulfate, borax (sodium tetraborate
ethylene diamine tetraacetic acid tetrasodium salt, trisodium
nitrilotriacetate and the like and mixtures of the foregoing.
Builder salt may be selected so as to provide either phosphate-
containing or phosphate-free detergents. As to the latter
embodiments, sodium carbonate is particularly effective.
Another material found to provide good detergency effects is
metakaolin which is generally produced by heating kaolinite
lattice to drive off water producing a material which is sub-
stantially amorphous by x-ray examination but which retains some
of the structural order of the kaolinite. Discussions of kaolin
and metakaolin are found in United States Patent 4,075,230 col-
umns 3 and 4 and Grimshaw, "The Chemistry of Physics of Clays
and Allied Ceramic materials," (4th ed., Wiley-Interscience),
pages 723-727. The metakaolin also appears to have softening
- 16 -
~2~34~S
utility. As to the latter, the most effective metakaolins
appear to be those which behave best in the reaction with sodium
hydroxide to form zeolite 4A as described in United States Patent
3,114,603 which refers to such materials as "reactive kaolin.'
As explained in the referenced sources, metakaolin is an
aluminosilicate. The metakaolin and/or a zeolite is included
in about the same amounts as the builder salt, and preEerably
supplemental thereto, e.g., zeolite silicate in a ratio of 6:1.
A particularly useful form of the metakaolin is that available
commercially as Satintone No. 2.
Preferred optional ingredients useful herein include
perfume such as Genie* perfume; optical brighteners and bluing
agents which may be dyes or pigments, suitable materials in this
regard including stilbene and Tinopal* 5BM brighteners and
particularly in combination and Direct Brilliant Sky Blue 6B,
Solophenyl Violet 4BL, Cibacete*, Brilliant Blue RBL and
Cibacete Violet B, Polar Brilliant Blue RAW and Calcocid Blue
2G bluing agents. The brightener may be included in amounts
ranging up to about 1% of the total composition while bluing
agents may range up to about .1% preferably up to about .01%
of total composition. Bluing agent, e.g., Polar Brilliant Blue
may be included in the soap spaghetti. In either case, the
amount need only be minimal to be effective.
Other ingredients of optimal significance include
bleaching agents which may be of the oxygen or chlorine libera-
ting type; oxygen bleaches include sodium and potassium perbor-
ate, potassium monopersulfate and the like, while chlorine
bleaches are typified by sodium hypochlorite, potassium dichloro-
isocyanurate, trichloroisocyanuric acid and the like. The
latter chlorine-liberating bleaches are representative of the
broad class of water soluble, organic, dry solid bleaches known
* Trade Marks - 17 -
~22:39~5
as the N-chloro imides including their alkali metal salts. These
cyclic imides have from about 4 to 6 members in the ring and are
described in detail in U.S. Patent 3,325,414. Each of the
oxygen and chlorine type bleaches discussed above are fully
compatible with the compositions herein and have good stability
in the presence of the anionic and cationic components. They
are generally used in proportions ranging from about 0.1 to
45% by weight of total solids or from about .05% to about 40%
based on total detergent composition.
Yet additional optional ingredients include water
soluble and/or dispersible hydrophobic colloidal cellulosic
soil suspending agent. Methyl cellulose, e.g., Methocel is
particularly effective. Polyvinyl alcohol is likewise effective
and especially in the washing of cotton and synthetic fibers
such as nylon, dacron and resin treated cotton. The additional
soil suspending agent may be included in amounts up to about
2% based on total solids and up to about 4% based on total
detergent composition. However, it must be emphasized that the
nonionic organic surfactant component of the soap spaghetti
supplies at least a major part of the anti-redeposition or
soil suspending function, its effectiveness in this regard being
significantly augmented by the soap material as previously
explained.
Fillers may also be included in addition to the afore-
mentioned ingredients, such as sodium sulfate, sodium chloride
and the like. The amount will range up to about 40% of total
composition.
The detergent composition is prepared by conventional
processing such as spray drying a crutcher mix of surfactant,
builder, filler etc. with volatile ingredien-ts such as perfume
or ingredients otherwise adversely affected by the spray drying
- 18 -
~L2~3~
process such as peroxygen bleach, e.g., sodium perborate. In-
gredients of this type are preferably post blended. As pre
viously mentioned, the soap spaghetti (when used) and cationic
softener-nonionic mixture are simply dry blended with the dried
detergent in particulate form by simple mechanical mixing which
is more than adequate to achieve a homogeneous product. As
previously explained, part or all of the soap spaghetti may
alternatively be added to the aqueous crutcher mixture. A
typical procedure would be as follows: Water is added to a
crutcher followed in order by anionic, sodium silicate,
optional ingredients where used such as Satintone #2 and filler
such as sodium sulfate and builder salt. The crutcher mixture
is heated to about 140F before addition of builder, e.g.,
sodium tripolyphosphate and the solids content of the crutched
mixture before spray drying is about 55-65%. Spray drying may
be carried out in a conventional manner by pumping the hot
mixture from the crutcher to a spray tower where the mixture
passes through a spray nozzle into a hot evaporative atmosphere.
Bleach and other materials remaining to be added are incorporated
into the cooled, dried detergent mass by any suitable means such
as simple mechanical mixing.
In use, sufficient of the detergent composition is
added to the wash cycle to provide a concentration of cationic
softener in the wash medium of about 1.5 to 8.0 g/3500g laundry
with a range from about 70 to the boil (i.e., about 212F). In
this connection it is understood that by "cold" wash is meant
a washing temperature of up to 70F, "warm" is from above 70F
to boiling.
Certain types of aliphatic quaternary ammonium com-
pounds though relatively ineffective as regards softening arenevertheless quite effective as antistats in the compositions
herein and particularly since they are physically compatible
-- lg --
~2~34~S
with anionic surfactant in liquicl environments. In general, such
materials encompass the ethoxylated and/or propoxylated
quaternary ammonium compounds of the following formula:
R ~ R~ X
wherein R7 and R8 represent ethoxy or propoxy, m and n are
integers of from 1 to 50 and may be the same or different and
R~ represents alkyl of 14 to 24 carbon. Compounds of this type
include (a) methylbis (2-hydroxy-ethyl) coco ammonium chloride
a liquid 75% active ingredient in isopropanol/water solvent and
avilable commercially as Ethoquad* c/12, Armak* and Variquat*
638, Sherex Chemical Co~; (b) Ethoquad c/25 - same as in (a)
but having 15 moles of ethylene oxide (m+n) and available as
95% active ingredient; (c) methylbis (2-hydroxyethyl) octadecyl
ammonium chloride, a liquid~ 75% active ingredient in isopro-
panol/water solvent available commercially as Ethoquad 18/12,
Armak and (d) same as (c) but having 15 moles of ethylene oxide
(m+n), a liquid, 95% active ingredient and available commercially
as Ethoquad 18/15, Armak. These materials can be used in amounts
ranging up to about 10% by weight of the total composition.
The following examples are given for purposes of
illustration only and are not intended to limit the invention.
All parts and percentages are given by weight.
* Trade Marks - 20 -
~.2~3~5
Example 1
A) 100 g. of powdered Arosurf TA (dimethyl distearyl
ammonium chloride~ are heated to 90C and a fluid melt results.
To this melt are added 10 g. of liquid nonionic Neodol 23-6.5
(C12 13 linear alcohol condensed with 6.5 moles of ethylene
oxide). The mixture is stirred well and then cooled to room
temperature. ~ white solid results. The solid is then ground
to a powder (on U.S. ~8 Sieve 0% through U.S. #100 Sleve < 10%).
The product resembles the original Arosurf powder.
B) Part A is repeated except that only 5 g. of
nonionic is used.
Example 2
The products of Example 1 as well as powdered cationic
alone (same as used for Example 1 to produce the co-melted
product), of a particle size the same as that of Example 1, are
each tested separately for dispersion uniformity in water by the
following procedure.
In a tergitometer equipped as usual with a recipro-
cating stirrer there are added to 500 ml of water (hardness of
150 ppm) at 70F (31C) 0.15 g. of a detergent (13.4% alkyl
benzene sulfonate; 24% sodium tripolyphosphate; 30% sodium sul-
fate; 4.5% sodium carbonate; 6.3% water soluble silicate solids;
7% moisture; ~% soap; minor amounts brightener, methocel and
perfume) which also contains 4.5% of the particles of Example 1.
The stirrer is operated for 5 minutes at 100 rpm and then the
aqueous composition is vacuum filtered through fresh smooth blue
denim fabric. In the case of the liquors with Example 1 -
containing detergent there is no visible (i.e., no white spots)
evidence of any residue. When the procedure is repeated using
identical conditions with the same composition except that in
place of 4.5% of Example 1 products, there is used 4.5% powdered
cationic alone there is a very visible pattern of white spotting
- 21 -
~2~3~
on the denim. This is very clear evidence of the outstanding
benefits of the Exarnple 1 products.
Example 3
When the compositions described in Example 2 are used
to wash soiled white towels in a washing machine and then dried
in an automatic dryer, the clothes in each instance are accept-
ably soft although those washed with the detergent containing
the Example 1 softener combination are somewhat softer. In
addition, the towels washed with the detergent containing
powdered cationic alone (i.e., not combined with nonionic) have
some visible albeit slight spotting (i.e., greasy staining~
due apparently to the cationic material whereas the others do
not.
Example 4
Example lA & lB & 3 are repeated except that the
following non-ionics are used in place of the Neodol 23-6.5.
a) Neodol 25-7
(A C12_15 alkyllinear alcohol + 7. moles of
ethylene oxide)
b) Igepal* C0-630
(Nonyl phenol + 10 moles of ethylene oxide)
c) Neodol 45-13
(A C14 15 alkyllinear alcohol + 13 moles of
ethylene oxide)
- Example 5
A spray dried heavy duty detergent having the
following composition is provided:
* Trade Marks - 22 -
~L2;~3~
Component Wt. %
-
Linear tridecylbenzene
sulfonate (LTBS) 15
Tripolyphosphate sodium
(NaTPP)
Silicate 7
Brightener (Stilbene* &
Tinopal* 5BM) .48
Q.S. sodium sulfate and water 44.52
100 . 00
To 90 g of the above composition are added 4 grams
of the cationic-nonionic powder of Example 1 part B. Excellent
results are obtained.
Example 6
Example 3 is repeated except that the detergent also
contains a soap spaghetti (4.5% in detergent).
Example 7
Example 6 is repeated except that the soap spaghetti
contains 20% by weight of Neodol 25-7.
In Examples 6 & 7 the soap spaghetti is an 85/15
tallow/coco soap.
Example 8
Example 3 is repeated but using a detergent composi-
tion having the following proximate analysis.
* Trade Marks - 23 -
~Z~3~L~5
Component Wt.
Linear dodecyl benzene sulfonate 23
2 3 20
Silicate 15
Borax 3
Nonionic surfactant
Soap 2
Carboxymethyi cellulose
Brightener * 0.48
Satintone
Na2SO4 and water Q.S.
*Stilbene and Tinopal 5BM
To 95 grams of the above composition, 5 gm of the
product of Example lB are added.
Example 9
Example 8 is repeated except 5 gm of a soap-nonionic
spaghetti (similar to Example 7) is used.
Example 10
Example 6 is repeated except that the soap spaghetti
used also contains 4~ by weight of carboxymethyl celluloseO
Example 11
The following heavy duty detergent composition is
prepared.
Component Wt. %
_.
Linear alkyl benzene sulfonate 9
Alcohol ether sulfate 8
Nonionic surfactant 2
Tripolyphosphate sodium 24
Zeolite A 17
Na~SO4, brightener, water Q.S.
To this composition is added 5.0 g of the cationic
* Trade Marks - 24 -
~2~3at05
product of Example lB.
Example 12
Example 11 is repeated except that the soap/nonionic
surfactant spaghetti of Example 6 is added to give 4% in the
detergent.
Example 13
An unperfumed powder detergent composition having the
following formulation is prepared.
Component Wt.
Linear tridecylbenzene sulfonate 14.8
Tripolyphosphate sodium 26.5
Silicate 6~9
Brightener (Stilbene* and Tinopal* 5 BM) 0.47
Sodium carbonate 4.9
Carboxymethyl cellulose 0.~5
Methocel* 0.6
Sodium sulfate, moisture Q.S.
To 90.6 parts by weight of the above unperfumed
powder detergent are added:
Cationic-Nonionic mixture of Ex lB 4.0 parts
Soap spaghetti ~90% tallow/coco
85/15; 10% Neodol 25-7 (Shell
Chemical Co.), spaghetti length =
15 mm, diameter = 0.5mm 4.0 parts
Borax Pentahydrate 0.7 parts
Nonionic surfactant
(Neodol 25-7) 0.5 parts
Perfume 0.2 parts
The following Examples illustrate the production and
use of the cationic-nonionic combination in prilled form.
*Trade Marks - 25 -
34~5
Example 14
Five hundred kilograms of dimethyl distearyl ammonium
chloride containing about 4% water is heated to 90C and forms
a melt. To this hot melt are added 25 kilograms of Neodol 23-
6.5. This co-melt is then sprayed downwardly from the top of
a 75-foot (about 24 meters~ tower - 16 foot diameter (about 5
meters). At the same time cool air at about 50F (10C) is
passed upwardly (i.e., countercurrent to the falling spray) at
a rate of about 30,000 cubic feet per minute (cfm). The con-
gealed product is collected at the bottom of the tower. Theproduct particle is white in appearance, free-flowing generally
spherical and solid. It has a porous surface (pock-marked
appearance). The bulk density of the prill is about 0.37(g/cc).
Example 15
To 95.5 g. of the detergent of Example 2 (without
Example 1 particles) are added 4.5 g. of the prills of Example
14.
Example 16
Example 5 through 13 are each repeated except that the
cationic-nonionic mixture used in those examples are replaced
by the prills of Example 14.
Example 17
Each of the previous examples is repeated except that
the nonionic in th~ cationic-nonionic mixture is used in amounts
of 2%; 7%; 12%; 15%; 20%.
Example 18
Each of the previous examples is again repeated
except that the cationic softener of the cationic-nonionic
mixture is replaced by the following:
- 26 -
3L;2~3~
(a) dimethyl di-tallow ammonium methosulfate
(b) dimethyl, di-hydrogenated tallow ammonium chloride
(c) methyl-l-tallow amido ethyl-2-tallow imidazolinium
methosulfate
(d) methyl-l-oleylamidoethyl-2-oleyl imidazolinium
methosulfate
Example 19
In each of the foregoing examples where the cationic
nonionic particles are used in admixture with the deteryent,
the amount of the cationic-nonionic is varied to provide 2%;
7% and 10% thereof based on the weight of the detergent
softener particles.
Among the nonionics which are useful in the cationic-
nonionic combination it is clear that there is a wide range of
melting point. Thus Neodol 23-6.5 is a liquid non-ionic as is
Igepal C0-630 (nonyl phenol plus 10 moles of ethylene oxide)
whereas Neodol 25-7 is a somewhat pasty solid and Neodol 25-12
a soft white solid. At higher ethylene oxide content (i.e.,
> 15 moles of ethylene oxide) the product becomes more solid
and somewhat waxy in feel and appearance.
Particularly where it is desired to use higher levels
(i.e., above about 5 to 10%) of nonionic in the cationic co-
melt, it is often advantageous to use a mixture of a liauid non-
ionic and a solid nonionic. In addition to the ethoxylated
solid noniOnics, one may also use other solid or pasty non-
ionics such as the glycerol mono and di-fatty glycerides. Of
particular value in this regard are glycerol mono-stearate,
glycerol mono-oleate and glycerol palmitate.
- 27 -
~3~
Example 20
Example lA is repeated except that half of the Neodol
nonionic is replaced by glycerol monostearate. In the test
procedure of Example 2 this product performs on a par with the
Example lA material.
Example 21
Example 3 is repeated using the product of Example 20
in place of the cationic materials of Example 3. Excellent
results are obtained.
Example 22
Example 7 is repeated except that the detergent con-
tains the tertiary softener combination of Example 20 in place
of the binary combinations of Example 1. The results are
simllarly excellent as those of Examples 3 and 7.
Example 23
-
Example 22 is repeated except that the nonionic used
is Neodol 45-11 (a C14 15 linear alkanol plus 11 moles of
ethylene oxide).
Example 24
Example 6 is repeated except that the soap spaghetti
is replaced by an equal weight of Carbowax* (MW-3000-8000)
crystals.
Example 25
Example 24 is repeated except that the amount of
Carbowax is varied as follows (~ in detergent):
ta) 0.5
(b) 1.0
(c) 2.0
(d) 4.0
* Trade Marks - 28 -
34C9~
Example 26
. . .
Examples 6, 7, 9, 10, 12, 13, 15, 17, 18, 19, 21, 22
and 23 are each repeated except where soap spaghetti is used it
is replaced by the Carbowax used in Examples 24 and 25 in the
amounts indicated (% based on weight of detergent).
(a) 0.2
(b) 0.4
(c) 0.8
(d) 1.0
(e) 2.0
(f) 3.0
(g) 5.0
Example 27
Examples 24, 25 and 26 are repeated using in place
of Carbowax the following:
(A) Pluronic F-10~ crystals
(B) Soap-spaghetti of high water solubility contain-
ing (a) 10 % sodium xylene sulfonate; (b) 20% sodium xylene
sulfonate; (c) 40% sodium xylene sulfonate.
The carbowax product of Examples 24 to 26 is a
polyethylene glycol. The Pluronic E-10~ of Example 27 is a
polyoxy propylene-polyoxyethylene block polymer containing 20%
polyoxy propylene groups as the hydrophobe and 80~ polyoxyethyl-
ene groups. The base hydrophobe has a MW of 3250.
The Pluronic F-108 is also illustrative of the water-
soluble nonionics which are useful in the cationic-r.onionic
co-melts of this invention~ Of particular value are the liquid
Pluronics containing up to about 50% polyoxyethylene groups and
a base hydrophobe molecular weight of the polyoxypropylene
moiety of from about 950 to 4000. Where combinations of, for
- 29 -
~Zq~3~
example, Neodol 23-6.5 and Pluronics are used, it may be
preferred to use pasty or solid Pluronics. These contain
generally from 25% to 80% of polyoxyethylene groups. Illustra-
tive of liquid Pluronics are Pluronic L-61, Pluronic L-64,
Pluronic L-72 and Pluronic 101; of the pasty Pluronics, we find
Pluronic P85 and Pluronic P105 among others; of the solid
products we may mention Pluronic F-87 and Pluronic F27.
~xample 28
As an illustratiion of the anti-stain benefits of the
present invention, several different soiled, white materials
are laundered at both 70F and 120F using the detergent con-
taining cationic alone, (A) on the one hand and the cationic-
nonionic prill of Example 14 on the other hand (B). The deter-
gent is that described in Example 2.
All of the white materials are equally soiled and the
reflectance values of laundered materials are measured. The
following are the reflectance values (Rd).
70F 120F
(A) (B) (A) (B)
Spun Dacron* 77.7 79.0 64.7 66.5
Dacron*/Cotton (65/35) 81.4 81.5 73.9 76.1
Cotton 87.8 87.8 87.3 87.3
Nylon 84.1 8502 84.1 84.5
The above clearly demonstrates that even after only
one washing there is significant improvement on Spun Dacron at
both laundering temperatures, on Dacron/Cotton at 120~F and on
Nylon at 70F. A difference of 0.5 Rd units is significant in
the sense that this difference is visually discernible.
- 30 -
