United States Patent (19) 11 4,140,641

Ramachandran 45) Feb. 20, 1979

54 CONCENTRATED LIQUID DETERGENT 56 References Cited
WTH FABRIC SOFTENER U.S. PATENT DOCUMENTS
3,537,993 11/1970 Coward ............................... 252/8.75
75 Inventor: Pallassana Ramachandran, 3,681,241 - 8/1972 Rudy ................................... 252/8.75
Robbinsville, N.J. 3,849,435 11/1974 Diery et al ... 252/8.75
3,920,565 11/1975 Morton. ... 252/8.75
3,951,879 4/1976 Wixon ...... ... 252/8.8
(73) Assignee: Colgate-Palmolive Company, New 3,959,157 5/1976 Inamorate - - -- ... 252/8.75
York, N.Y. 3,974,076 8/1976 Wiersema et al. .................. 252/8.75
Primary Examiner-William E. Schulz
Attorney, Agent, or Firm-Herbert S. Sylvester; Murray
(21) Appl. No.: 887,788 M. Grill; Norman Blumenkopf
22 Fed Mar 17, 1978 57 ABS CT
22 Filed: a A highly concentrated single phase liquid detergent
composition containing fabric softener is formulated
51) Int. Cl” ............................................ D06M 13/36 from a nonionic surfactant and an imidazolinium quater
52 U.S. C. .................................... 252/8.75; 252/8.7; nary ammonium fabric softener.
252/8.8
58) Field of Search ......................... 252/8.75, 8.7, 8.8 9 Claims, No Drawings
 4,140,641 2
1
is half the amount generally required for concentrated
CONCENTRATED LIQUID DETERGENT WITH liquid laundry detergents,
FABRIC SOFTENER The nonionic surfactants for use in compositions ac
cording to the present invention are commercially
BACKGROUND OF THE INVENTION 5 known and comprise the water soluble products which
This invention relates to detergent compositions hav are derived from the condensation of an alkylene oxide
ing superior detergent and fabric softening properties. or equivalent reactant and a reactive-hydrogen hydro
In the fabric softening art, it is well known to prepare phobe. The hydrophobic organic compounds may be
fabric softening formulations which are adapted for use aliphatic, aromatic, or heterocyclic, although the first
in the rinse cycle of conventional home-laundry wash 10 two classes are preferred. The preferred types of hydro
ing machines. As a general rule, any one of a wide phobes are higher aliphatic alcohols and alkyl phenols,
variety of softening agents may be used, and they are although others may be used such as carboxylic acids,
normally formulated as dispersions in water containing carboxamides, mercaptans, sulfonamides, etc. The eth
from about 4% to about 7% of the active ingredients. ylene oxide condensates with higher aliphatic alcohols
It has been recognized for some time that it would be 15 represent a preferred class of nonionic compounds.
desirable as a matter of convenience to employ the Usually the hydrophobic moiety should contain at least
fabric softening formulation concurrently with the de about 6 carbon atoms and preferably at least about 8
tergent in the wash cycle of the washing machine. In carbon atoms, and may contain as many as about 50
many of the home laundry washing machines now in carbon atoms or more. The amount of alkylene oxide
use, the machine is so designed that in order to use a 20 will vary considerably depending upon the hydro
rinse cycle fabric softener it is necessary for the house phobe, but as a general rule at least about 5 moles of
wife to watch the cycle carefully, and to interrupt the alkylene oxide per mole of hydrophobe should be used.
cycle just before the final washing step to add the fabric The upper limit of alkylene oxide will vary also, but no
softening agent, because no special provision has been 25 particular criticality can be ascribed thereto. As much
made for dispensing fabric softeners at the time of the as 200 or more moles of alkylene oxide per mole of
final rinse. The use of fabric softeners in such machines
hydrophobe may be employed. While ethylene oxide is
manifestly would be made considerably more conve the preferred and predominating oxyalkylating agent,
other lower alkylene oxides such as propylene oxide,
nient if it were possible for the housewife to add the butylene oxide, and the like may be used or substituted
fabric softener together with the laundry detergent, 30 in part for the ethylene oxide.
whereby the softener would act concurrently with the Other nonionic compounds which are suitable are the
detergent simultaneously to wash and to soften the polyoxyalkylene esters of the organic acids such as the
fabrics. higher fatty acids, the resin acids, tall oil acids, acids
Conventional fabric softening formulations can be from petroleum oxidation products, etc. These esters
used as wash-cycle softeners. However, in order to 35 will usually contain from about 10 to about 22 carbon
obtain a reasonable amount of softening it is necessary atoms in the acid moiety and from about 12 to about 30
to use generally in the order of twice the normal moles of ethylene oxide or its equivalent.
amount of formulation. Because this would require the Still other nonionic surfactants are the alkylene oxide
housewife to maintain large quantities of fabric soften condensates with the higher fatty acid amides. The fatty
ing formulations on her shelves, and would involve an acid group will generally contain from about 8 to about
apparently wasteful use of fabric softeners, housewives 22 carbon atoms, and this will be condensed with about
are reluctant to employ the fabric softening formula 10 to about 50 moles of ethylene oxide. The correspond
tions currently available as washcycle softeners. ing carboxamides and sulfonamides may also be used as
To overcome this difficulty, it would be desirable to substantial equivalents.
provide a concentrated composition containing both 45 The oxyalkylated higher aliphatic alcohols are the
detergent and fabric softener which, when used in a preferred nonionic surfactants for compositions accord
small quantity, would provide effective cleaning and ing to the present invention. The fatty alcohols should
softening of fabrics in the home laundry machine. For contain at least 6 carbon atoms, and preferably at least
this purpose, a formulation having a very high concen about 8 carbon atoms. The most preferred alcohols are
tration of active ingredients would be needed. It has not lauryl, myristyl, cetyl, stearyl, and oleyl alcohols, and
been possible heretofore to prepare one-phase liquid the said alcohols should be condensed with at least
compositions employing the commercially accepted about 6 moles of ethylene oxide. A typical nonionic
fabric softeners and detergents available. The generally product is C12-C13 aliphatic alcohol condensed with
effective fabric softeners which have found widespread about 6.5 moles of ethylene oxide. The corresponding
commercial acceptance, such as the di-(higher alkyl)-di 55 alkyl mercaptans when condensed with ethylene oxide
(lower alkyl) ammonium salts, cannot be formulated are also suitable in the compositions of the present in
into one-phase liquid compositions which are stable at vention.
high concentrations. Using the typical commercially The alkoxylated higher aliphatic alcohols are particu
available fabric softening agents, formulations contain larly well suited for home laundry detergent formula
ing a maximum of 7% to 8% active ingredient can be tions because they are readily biodegradable and com
prepared without incurring stability difficulties. patible with cationic surfactants and fabric softeners
and with most other adjuvants.
SUMMARY OF THE INVENTION It has been found that only two fabric softeners can
A highly concentrated single phase liquid detergent be used in the highly concentrated single-phase deter
composition containing fabric softener has been formu 65 gent softener compositions according to the present
lated using a nonionic surfactant and a quarternary invention: methyl (1) oleyl amido ethyl (2) oleyl.
imidazolinium fabric softener. The product is recom imidazolinium methyl sulfate, and methyl (1) tallow
mended for use at levels of cup per washload, which amido ethyl (2) tallow imidazolinium methyl sulfate.
 3
4,140,641.
4.
The 1-methyl-1-alkylamidoethyl-2-alkylimidazolin solution, BRV solution, DCR liquid, DCBVF, EV
ium methosulfate is generally obtained in concentration liquid, DBS liquids, and ANR.
of 75% active ingredient in isopropanol. This is a low It was found that anionic tetrasulfonated stilbene type
viscosity, clear liquid system. The 1-methyl-1-tallowa brighteners gave a better whitening effect than the
midoethyl-2-tallowimidazolinium methosulfate also is disulfonated type of brighteners in combination with
generally obtained in a concentration of 75% active the cationic fabric softeners of the present invention.
ingredient in isopropanol. This system is a liquid at 80 Specific examples of these disulfonated tetrasulfonated
F. brighteners are Phorwhite BKL, BUP, BBU solution,
The fabric softeners for use in the present invention and BRU solution.
give fabrics a soft and fluffy feed while imparting good 10 Other types of optical brighteners which give supe
rewettability. These fabric softeners are substantive to rior whitening effects in combination with the cationic
fabric and help to reduce static cling and wrinkling softeners of the present invention are those components
making fabrics easier to iron and more comfortable to having no sulfonate moieties. The preferred class of
Wea.
brighteners for use in the present invention include the
The solvent medium for the instant liquid detergent 15 2-(4-styrylphenyl)-2H-naphthol,2-d triazoles, 4,4'-
composition is an aqueous one, and may be water alone bis(1,2,3-triazol-2-yl)stilbenes, 4,4'-bis(styryl) bisphe
or may be substantially water with additional solvents nyls, and the 7-aminocoumarins. Specific examples of
added for particular ingredients. Because of the avail these brighteners include 4-methyl-7-diethylamino cou
ability of water and its minimum cost, it is preferred to marin, 1,2-bis(benzimidazol-2-yl)ethylene, and the 1,3-
use water as the major solvent present. Yet, amounts of 20 diphenyl-phrazolines, as well as 2,5-bis(benzoxazol
other solvents, generally up to 20%, and preferably a 2-yl) thiophene, 2-styryl-naphth (1,2-d) oxazole, and
maximum of 15% of the total content, may be used. 2-(stilben-4-yl)-2H-naphtho(1,2-ditriazole.
Generally, such a supplementing solvent will be either a The concentration ranges of the nonionic surfactant
lower alkanol or a lower diol or polyol, e.g., ethanol, are from about 40% to about 70% by weight, with 60%
isopropanol, ethylene glycol, propylene glycol, glyc 25 being preferred. The concentration of the fabric soft
erol, or the like. Nevertheless, etheric polyols such as ener is from about 15% to about 30% by weight, with
diethylene glycol and those known as cellosolves may about 21% being preferred. The aqueous solvent me
also be used. dium, preferably water, but which may also contain
Various selected compatible adjuvants may be pres mono-, di-, and polyhydric alcohols and similar sol
ent in the liquid detergent composition to give it addi 30 vents, will range from about 5% to about 55% by
tional desired properties, either of functional or aes weight. The optical brightener content of the liquid
thetic nature. Thus, there may be included in the formu composition will normally be from about 0.2% to about
lation: soil-suspending or anti-redeposition agents, e.g., 3.0%, and preferably from 0.25 to 2.7%. Such concen
polyvinyl alcohol sodium carboxymethyl cellulose, trations are soluble in the described liquid detergents
hydroxypropyl methyl cellulose, optical brighteners, 35 and are effective in noticeably brightening the washed
e.g., cotton, amide, and polyester brighteners; preserva clothing.
tives, e.g., methyl parasept or sodium benzoate; ultravi The contents of the other adjuvants is preferably
olet absorbers, and perfumes. The adjuvants, of course, maintained at less than 5% by weight of the product.
will be chosen to be compatible with the main constitu Use of more than the described proportions of the such
ents of the detergent formulation. compounds can often significantly change the proper
Of the adjuvants mentioned perhaps the most impor ties of the liquid detergent, and therefore should be
tant for functional effect are the optical brighteners avoided.
because the modern housewife has come to expect that Although the detergent softener composition of the
washed clothing will no longer merely be clean and present invention is a stable, clear one-phase liquid, a
white but will also be bright in appearance. The optical 45 compatible opacifying agent may be added to impart a
brighteners are substantive to textiles being washed creamy appearance to the formulation.
(such substantivity may be selective) and sometimes are Use of the present liquid detergent-softener is both
of comparatively low solubilities. Accordingly, it is simple and exceptionally efficient. As the formulation is
important that they be maintained in solution in the extremely concentrated, very small amounts of liquid
liquid detergent composition and, even more important, 50 are employed, and the product can be used in both top
they must be immediately dispersed in the wash water loading and front loading washing machines. For exam
so as to avoid producing a wash containing noticeable ple, using a typical formulation of the present invention,
brightened spots, rather than a uniformly bright appear only about cup of liquid is needed for a full automatic
ance. Here, the choice of brightener to obtain best re washing machine tub of wash, wherein the water vol
sults will be ascertainable to one of skill in the art. It has 55 ume is from 15 to 18 gallons. Correspondingly, only
been found that relatively small quantities of brighten 1/16 cup is used when a front loading washing machine
ers should be used, so as not to exceed the limits of of about half the volume of the top loading machine.
solubilities. Also, within the class of these materials Thus, the concentration of liquid detergent in the wash
certain brighteners have been found to be especially water is only about 6 grams of softener and 18 grams of
readily dissolved, and thus are suitable for incorpora nonionic surfactant. .
tion in these products. Fortunately, such preferred The wash water used may be a fairly soft water or
brighteners include both cotton and amide-polyester water of reasonable hardness, and will generally be used
brighteners, making them suitable for use with laundries at elevated temperature. The composition of the present
containing a variety of material and synthetic materials. invention is also useful in laundering clothes in very
Among the commercial brighteners that are used in the 65 hard waters and at lower temperatures. Thus, water
present system are Tinopal UNPC, Tinopal CBS (Ciba hardness may range from 0 to over 300 parts per million
Geigy), Arctic White CC (Hilton Davis), and the fol calculated as calcium carbonate, and washing tempera
lowing Phorwhites from Verona: BKL, BUP, BBC tures may be from 40' to 120 F. Washing will be ef
 4,140,641
5 6
fected in an automatic washing machine in which the DETAILED DESCRIPTION OF THE
washing is followed by rinsing and spin or other drain INVENTION
ing or wringing cycles or operations. Of course, the
detergent composition may also be used for hand wash 5 The following specific examples illustrate various
ing of laundry, in which case it may sometimes be used embodiments of the present invention. It is to be under
full strength on certain stains on the laundry, or the stood, however, that such examples are presented for
laundry may be soaked in a higher concentration solu purpose of illustration only, and the present invention is
tion of detergent before washing. in no way to be deemed as limited thereby.
The washing operations will generally take from 10 EXAMPLE
three minutes to one hour, depending on the fabrics A detergent-softener composition was prepared by
being washed and the degrees of soiling observed. After blending together the following ingredients:
completion of washing and the spinning, draining or
wringing operations, it is preferred to dry the laundry in
an automatic dryer soon thereafter but line drying may 5 %
by weight
also be employed.
The present detergent softener composition dissolves Neodol 23-6.5IC12-13 ethoxylated (6.5EO) alcohol)
Methyl (1) oley amido ethyl (2) oleyl imidazolinium
60
26.7
very easily in the wash water is warm or cold, and very methylsulfate 75% AI (Varisoft 3690, Ashland)
Water 11.9
effectively cleans, softens and eliminates static charge Polar BrilliantBlue 0.5% solution 0.4
on clothing and other items of laundry without impart 20 Perfume 1.0
ing a water repellant finish thereto. It may be used in
either top loading or front loading washing machines White cotton towels (16'x26' obtained from J. C.
and may be desirably adjusted to foam to the correct Penney & Co.) were washed for ten minute wash cycles
extent. The product is an attractive clear, stable liquid 25 in a General Electric washer in 17 gallons of tap water,
which maintains its activity and uniformity over a long having a hardness of 100 ppm, at 120 F, using cup of
shelf life. In tests in which the effects of using it are the above detergent softener formulation. After being
compared to those from the employment of commercial rinsed and air dried, the towels were rated for softness
heavy duty laundry detergents, it is rated very favor on a scale of 1 = no softness to 10=excellent softness.
ably. It is often preferred for convenience of use be 30 The towels washed according to the above had a soft
cause of its high concentration and elimination of a ness rating of 8 to 10, and appeared to be very clean.
separate softening step; and excellent detergency, soft The detergent formulation of Example I was com
ening, anticling and rewettability properties are ob pared with a conventional, less highly concentrated
served. liquid detergent.
This product may be prepared by simply admixing 35
the various ingredients at room temperature with agita % by weight
tion to ensure solubilization thereof in the aqueous me Softened water 10
dium. The order of addition of ingredients and the tem SD3A alcohol 7
perature of compounding may be varied without ad Tinopal CBS
Phorwhite BHC'
0.44
0.147
versely affecting the formation of the single phase, clear Triethanolamine 9% AI 0,474
liquid product of instant invention. Na linear alkyl (C10-13) benzene sulfonate
Neodol 23-6.5
14.238
33.39
Where clear, one-phase liquids are desired, the con Sodium formate 1.52
centrations of the active ingredients can be varied only Blue color solution 0.3
with certain limits. Thus, the concentration of the soft Perfume 0.3
45 Softened water 32.261
ener cannot be much greater than 30% if a clear liquid '4,4'-bis(o-sulfostyrylbiphenyl
is desired. '4,4'-bis(4-phenyl 2H-1,2,3-triazol-2-yl)-2,2'-stilbene dipotassium sulfonate.
The liquid detergent-softener composition of the
present invention exhibits many desirble characteristics Soiled 3x4' cotton cloths were washed in a General
which regard to both physical properties and perfor Electric washer in 17 gallons of tap water, having a
mance in use. As to its physical properties, the composi 50 hardness of 100 ppm, at 120 F., for a ten minute wash
tions are pourable and free-flowing from the container cycle. After being rinsed and air dried, the reflectance
as manufactured and after aging. They exhibit a high values of the cloths were measured, expressed in Rd
degree of stability upon storage at normal room temper units. The results are tabulated below:
ature of the order of about 70 F. over a period of many TABLE I
months without any appreciable precipitation. As a 55 Reflectance values, Rd units
result, the consumer can utilize them conventionally by detergent of conventional
addition of very small portions to a laundering bath, and Example I detergent
the detergent and softener will be present in constant cup cup
composition in each portion. While compatible adju 60 Test fabric cotton
Clay on cotton
41.4
68.6
38.2
64.3
vant materials may be added to render the final product Clay on PE/cotton 71.5 63.9
translucent or opaque as desired, the requirement for a EMPA cloth (soiled with 22.7 21.7
one-phase solution of the main ingredients insures that olive oil and carbon black)
effective washing and softening power will be obtained
with each portion and promotes the stability and homo Cloths washed according to the above in the deter
geneity of the product. The liquid may be packaged in gent-softener formulation of Example I had a softness
any suitable container or packaging material such as rating of 9, and evidenced no cling or static electricity
metal, plastic, or glass. buildup. Cloths washed in the conventional liquid deter
 4,140,641
7 8
gent had a softness rating of 1, and evidenced both
clinging and static buildup. EXAMPLE V
It can be seen from the above that the detergent for A clear, one-phase liquid softener-detergent is pre
mulation of Example I provides effective cleaning and pared by blending together the following ingredients:
softening while requiring the use of only half as much as 5
conventional liquid detergents. % by weight
The detergent-softener composition was compared to Tergitol 25-L9 (C1-C5 ethoxylated 70
the above-identified conventional liquid detergent in a (9 moles EO) linear alcohol)
standard mixed soil washing. Swatches of fabric, 3"x4" Methyl (1) oleyl amido ethyl (2) oleyl 25
imidazolinium methyl sulfate 75% AI
were subjected to standard soils and washed as above in 10 Water 4.
water at 100 F. with a hardness of 100 ppm. The results Tinopal
Perfume
CBS
0.55
0.45
are tabulated below:
TABLE II
Reflectance Values (Rd units 15 This composition is effective when used in concentra
Detergent of Conventional tions of cup per full washload.
Example I Liquid Detergent
Test fabric nylon 45.9 64.5 EXAMPLE VI
Test fabric cotton 42.1 45.2 A clear, one-phase liquid softener-detergent is pre
Clay soil on cotton 72.3 7.7
Clay soil on polyester pared by blending together the following ingredients:
cotton PP 73.7 64.3 2O
EMPA soil 20.9 21.9
% by weight
Neodol 23-6.5 60
EXAMPLE II 1-methyl-1-tallowamidoethyl-2- 20
tallowimidazolinium methosulfate, 75% AI
A clear, one-phase liquid softener-detergent is pre- 25 Water
Propylene glycol
16
2
pared from the following: Perfume 1
2,5-bis(benzoxazol-2-yl)thiophene 1
% by weight
Tergitol 15-S-7ethoxylated C1-C15 linear 50 What is claimed is:
alcohols (7 moles EO 1
Methyl (1) oley amido ethyl (2) oley 30
3O 1. A single-phase liquid detergent-softener composi
imidazolinium methyl sulfate 75% AI tion comprising:
Water
2,5-bis(benzoxazol-2-yl)thiophene brightener
18.6
0.4
(a) from about 40% to about 70% by weight nonionic
Perfume 1.0 surfactant;
35 (b) from about 15% to about 30% by weight of a
softener selected from the group consisting of
EXAMPLE III methyl (1) oleylamido ethyl (2) oleyl
imidazolinium methyl sulfate and 1-methyl-1-tal
A clear, one-phase liquid softener-detergent is pre lowamido-ethyl-2-tallowimidazolinium methosul
pared from the following: 40 fate;
(c) a solvent.
% by weight 2. The detergent-softener composition of claim 1
Neodol 23-6.5 wherein the softener is methyl (1) oleyl amido ethyl (2)
. 55
i-methyl-l-tallowamidoethyl-2- imidazolinium sulfate methyl.
26
tallowimidazolinium methosulfate, 75% A
Water 13 45
3. The detergent-softener composition of claim 2
Isopropanol 5 wherein the softener is present in an amount of 21% by
Tinopal CBS 0.5 weight.
Perfume 0.5 4. The detergent-softener composition of claim 3
wherein the nonionic surfactant is present in the amount
EXAMPLE IV
of 60% by weight.
50 5. The detergent-softener composition of claim 2
An opaque one-phase liquid softener-detergent is wherein the nonionic surfactant is an ethoxylated linear
prepared from the following: aliphatic alcohol.
6. The detergent-softener composition of claim 5
wherein the nonionic surfactant is a C12-C13 alcohol
% by weight 55 ethoxylated with 6.5 moles of ethylene oxide.
Tergitol 15-S-7 60 7. The detergent-softener composition of claim 1
1-methyl-l-tallowamidoethyl-2- 30
tallowimidazolinium methosulfate, 75% AI including a compatible optical brightener.
Water
Propylene Glycol
4.7
3 8. The detergent-softener composition of claim 1
Castor wax 60 wherein the solvent is water.
Polar brilliant blue, 1.5% solution
Perfume
0.3
1.0
9. The detergent-softener composition of claim 1
wherein the solvent is a mixture of water and a solvent
selected from the group consisting of water-soluble
This composition is effective for cleaning and soften lower alkyl monohydric alcohols, dihydric alcohols,
ing when used in concentrations of cup per full wash and polyhydric alcohols.
load. 65
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 4,140,641.
DAED February 20, 1979
INVENTOR(S) : Palassana Ramachandran
It is certified that error appears in the above-identified patent and that said Letters Patent
are hereby corrected as shown below:

In Claim 2, third
--olleyl--; secondline after "(2)",
line, "sulfate methyl"insert
should
read --methyl sulfate--.
signed and sealed this
Sixth Day of January 1981
SEAL
Attest:

SIDNEY.A. DAMOND
Attesting Officer Companissioner of Patents and Trademarks