U.S. patent number 3,915,867 [Application Number 05/353,981] was granted by the patent office on 1975-10-28 for domestic laundry fabric softener.
This patent grant is currently assigned to Stepan Chemical Company. Invention is credited to Hyung H. Kang, Edward A. Knaggs, Rodger G. Peters.
United States Patent |
3,915,867 |
Kang , et al. |
October 28, 1975 |
Domestic laundry fabric softener
Abstract
A self-emulsifying domestic laundry fabric active softener base
comprised of N-methyl, N,N-di-(.beta.-C.sub.14 - C.sub.18 -acyloxy
ethyl), N-.beta.-hydroxy ethyl ammonium metho sulfate characterized
by good softening, outstanding whiteness-retention and excellent
rewetting properties and has a light color having an index on the
Gardner scale in the range of about 1 to 2. The active softener
base is dispersed in an inert vehicle such as isopropanol and/or
water and may be intermixed with other additives, such as perfumes,
nonionic wetting agents, optical brighteners, etc.
Inventors: |
Kang; Hyung H. (Evanston,
IL), Peters; Rodger G. (Arlington Heights, IL), Knaggs;
Edward A. (Deerfield, IL) |
Assignee: |
Stepan Chemical Company
(Northfield, IL)
|
Family
ID: |
23391412 |
Appl.
No.: |
05/353,981 |
Filed: |
April 24, 1973 |
Current U.S.
Class: |
510/525; 554/91;
554/110; 510/522 |
Current CPC
Class: |
D06M
13/463 (20130101); C11D 3/001 (20130101); C11D
1/62 (20130101) |
Current International
Class: |
C11D
3/00 (20060101); D06M 13/00 (20060101); D06M
13/463 (20060101); C11D 1/38 (20060101); C11D
1/62 (20060101); D06M 013/00 (); D06M 015/00 () |
Field of
Search: |
;252/8.8,8.75
;260/404,567.6R,402.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Chemistry & Industry, July 5, 1969, pp. 893-903..
|
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Walsh; Donald P.
Attorney, Agent or Firm: Hill, Gross, Simpson, Van Santen,
Steadman, Chiara & Simpson
Claims
We claim as our invention:
1. A self-emulsifying domestic laundry fabric softener agent
consisting essentially of a mixture comprised of
N-alkyl-N,N-di-(.beta.-C.sub.14 - C.sub.18 -acyloxy ethyl),
N-.beta.-hydroxy ethyl ammonium compounds and a substantially inert
vehicle, said agent being characterized by good fabric softening,
whiteness-retention and rewetting properties and by a light color
index on the Gardner scale in the range of about 1 to 2, said
C.sub.14 - C.sub.18 acyloxy group comprised of a mixture of
substantial amounts of palmitic, stearic and oleic radicals.
2. A softening agent as defined in claim 1 wherein said agent is
N-methyl, N,N-di-(.beta.-C.sub.14 - C.sub.18 -acyloxy ethyl),
N-.beta.-hydroxy ethyl ammonium metho sulfate.
3. A softening agent as defined in claim 1 wherein said inert
vehicle includes water.
4. A softening agent as defined in claim 1 wherein said inert
vehicle includes isopropanol.
5. A softening agent as defined in claim 1 wherein said inert
vehicle comprises a mixture of isopropanol and water.
6. A softening agent as defined in claim 1 wherein said inert
vehicle is selected from the group consisting of a C.sub.1 -
C.sub.4 aliphatic alcohol, a C.sub.1 - C.sub.4 aliphatic glycol, a
C.sub.1 - C.sub.10 aliphatic alcohol alkali sulfate, an alkyl
benzene alkali sulfonate, water and mixtures thereof.
7. A softening agent as defined in claim 1 wherein said mixture
includes about 75% by weight of said agent and about 25% by weight
of said inert vehicle.
8. A softening agent as defined in claim 1 wherein said mixture
includes about 8% by weight of said agent and about 92% by weight
of said inert vehicle.
9. A method of softening domestic laundry fabrics comprising
treating said fabrics in an aqueous media containing an amount of
cationic quaternary ammonium softener agent comprising
N-methyl-N,N-di-(.beta.-C.sub.14 - C.sub.18 -acyloxy ethyl),
N-.beta.-hydroxy ethyl ammonium metho sulfate.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to fabric softeners and more particularly to
light colored self-emulsifying domestic laundry fabric softeners
which exhibit excellent rewetting and whiteness-retention
characteristics.
2. Prior Art
A large number of domestic laundry fabric softeners which generally
include cationic quaternary compounds are known, and reference is
made to W. P. Evans, "Cationic Fabric Softeners", Vol. 5, Chemistry
and Industry, July 1969, pages 893-903 for a general discussion
thereof. Repeated use of such quaternary softeners tends to
discolor or yellow fabrics, causing user dissatisfaction. This
yellowing characteristic is particularly noticeable when the
fabrics are laundered with nonionic detergents at high pH levels. A
nonionic containing detergent composition built with sodium
carbonate is an example of a detergent material which tends to
produce severe yellowing. Further, repeated use of at least certain
known softeners tend to waterproof fabrics causing laundering
difficulties.
Laundry-related products, especially those which are intended for
domestic use, are judged by consumers for effectiveness on the
basis of various factors, including the color of the product. A
consumer generally assumes that if a product has a light color, it
will be less likely to yellow clothes. A light colored product is
generally equated with white colored fabrics after washing.
Softeners having a white color, as opposed to a creamy or yellowish
color are not readily available. Some manufacturers have either
attempted to convince consumers that blue or green colored products
are desirable as white products but in fact have incorporated
coloring agents, bleaches, dyes, optical brighteners to mask less
appealing creamy or yellowish colors. The consumers have generally
resisted accepting offwhite products and the addition of various
coloring agents have, at best, only achieved an approximation of
the desired whiteness and merely increased the cost of the ultimate
product.
Prior art workers have suggested that various surfactants of the
general class comprising condensation products of alkylol amines
and higher fatty acids quaternized with various quaternization
reagents, such as dimethyl sulfate, diethyl sulfate, methyl
chloride, etc., have some softening properties and that such
surfactants may be capable of functioning either as commercial
textile lubricants or as domestic softening agents. However, such
surfactants either do not perform as expected, discolor fabrics,
lessen rewetting of the fabrics, require various additives for
successful domestic applications or are themselves of a color
unappealing to domestic users.
SUMMARY OF THE INVENTION
The invention provides an economical self-emulsifying domestic
laundry fabric softener which does not discolor fabrics or prevent
rewetting thereof with repeated use and which is characterized by a
clean light color.
It is a novel feature of the invention to provide a selfemulsifying
domestic laundry fabric softener agent comprised of a mixture of
N-alkyl-N,N-di(.beta.-C.sub.14 - C.sub.18 -acyloxy ethyl),
N-.beta.-hydroxy ethyl quaternary ammonium compounds and an inert
vehicle thereof; which agent is characterized by a light color
having an index on the Gardner scale in the range of about 1 to
2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The domestic laundry fabric softeners of the invention are
characterized by excellent fabric softening properties, excellent
whiteness-retention (non-yellowing) properties, outstanding
rewetting characteristics and are of a consumer-appealing light
color. The light color of the instant softeners should be
differentiated from the whiteness and non-yellowing property
imparted to the laundered fabrics with which such softeners are
used.
The rewetting characteristics of the fabric softeners of the
invention allow fabrics treated thereby to be easily rewetted with
aqueous solutions, such as encountered in domestic laundering
operation. Conventional softeners are generally combined with
various rewetting agents to prevent "waterproofing" softener
treated fabrics. The softeners of the invention do not require any
rewetting agents and exhibit improved rewetting characteristics
over conventional fabric softening formulations which include
rewetting agents. Further, the fabric softeners of the invention
are self-emulsifying and require no auxiliary emulsifying agents,
such as conventional nonionic surface-active agents. Studies have
shown that while active softeners of the invention are compatible
with nonionics, generally insufficient benefits result for
economical justification to include nonionics in softeners
formulations utilizing the active softener of the invention.
The light color characteristic of the softeners of the invention
render formulations based thereon appealing to consumers. While a
dark color of a softener does not necessarily indicate that it is
inefficient or will discolor fabrics, nevertheless, consumers
prefer light color softeners for domestic laundry usage.
The fabric softeners of the invention are prepared from a C.sub.14
- C.sub.18 fatty acid alkyl ester mixture, preferably methyl
esters. These fatty methyl ester mixtures are staple articles of
commerce and their synthesis is well known so that no further
explanation thereof is required. In the preferred embodiments, the
softeners of the invention is formed from 2 molecules of the above
fatty acid alkyl ester mixture, which for practical purposes is a
mixture of oleic, palmitic, stearic acid alkyl esters, along with
minor amounts of other fatty material constituents. Generally,
these materials are hydrophobic, especially the saturated entities
and require the addition of hydrophilic groups thereto for
effective use in aqueous systems. Quite unexpectedly it was found
that two molecules of a C.sub.14 - C.sub.18 fatty ester mixture,
(which is primarily comprised of oleic, palmitic, and stearic acid
methyl esters) when combined with triethanolamine and quaternized
yield a product which is very light colored, is a good softener,
and exhibits excellent whiteness-retention and rewetting
properties.
The self-emulsifying fabric softeners of the invention form stable
suspensions over a wide temperature range and can be diluted as
desired without phase separation or the like. The active softener
of the invention is, in undiluted form, a somewhat viscous gel or
solidlike mass which is not readily handleable and must be combined
with minor amounts of an inert vehicle for either fabric base
formulation or for domestic formulation. For a fabric base
formulation (after synthesis and prior to packaging for consumer
usage), an C.sub.1 - C.sub.4 aliphatic alcohol, C.sub.1 - C.sub.4
aliphatic glycol, C.sub.1 - C.sub.10 aliphatic alcohol alkali
sulfate, urea, alkyl benzene alkali sulfonates, water, other
similar hydrotropic agents and mixtures thereof provide a suitable
vehicle. Although from a point of economic availabillity, lack of
disagreeable odors, compatibility with laundering environments,
etc., water, isopropanol and mixtures thereof are preferred. For
consumer or domestic formulations, water is a preferred vehicle for
obvious reasons and any amount of water can be intermixed with the
fabric base formulation. For a fabric base formulationo one of the
enumerated organic vehicles, such as isopropanol is preferred since
a relatively concentrated formulation is preferred.
In preparing softener base formulations which include the active
softener of the invention, it has been noted that a ratio of active
softener to vehicle of about 3:1 provides a practical solution.
Larger amounts of vehicle and/or softener may be utilized, but as a
practical matter a mixture of about 75% by weight of softener and
about 25% of vehicle, such as isopropanol, is preferred.
In preparing softener formulations for domestic use, a ratio of
active softener to vehicle of about 1:10 or 20 provides a practical
solution in the retail sales field. Again, larger amounts of
vehicle and/or softener may be utilized, but as a practical matter
about 0.1% by weight active fabric softener based on weight of
fabrics is sufficient in actual wash machine use. Generally, a
mixture of about 6% to 8% by weight of softener and about 92% to
94% by weight of vehicle is often sold in the market place. As
indicated earlier, preferred vehicles include isopropanol, water
and mixtures thereof.
The active softener of the invention is, in its solidified form, an
attractive clean, light color, which on the Gardner scale has a
color index of about 1 to 2. As will be understood by workers in
the art, the Gardner scale here referred to is based on a
Gardner-Hellige colorimeter. The Gardner color scale is a
designated scale to aid one in subjectively determining the color
of a given substance. It ranges in value from 1 to 18 in
designating light to dark colors. The softeners of the invention
have a milky-white color in 6% to 8% formulations, which comprise
the typical domestic consumer formulations. The Gardner color scale
is not directly usable on such consumer formulations since they are
emulsions as contrasted to clear solutions. However, the softeners
of the invention are readily placed in clear solution by
intermixing a fairly small amount (i.e. about 25% by weight) of an
organic vehicle, such as isopropanol or ethanol with a fairly large
amount (i.e. about 75% by weight) of the active softener and
heating the resultant mixture to about 55.degree.C. whereupon the
solution becomes clear and is suitable for color comparison on the
Gardner scale. Accordingly, the term "color index on the Gardner
scale" as utilized herein and in the claims will be understood to
refer to the value attained when a clear solution containing about
75% solids in about 25% isopropanol or the like is read at about
55.degree.C. It should also be pointed out that a clear solution of
a material may have a Gardner scale index of 8 or 9 and be of a
brown color. The active softener of the invention has a Gardner
color index of about 1 to 2 and, in a clear solution, has the
appearance of a water-white solution but in an emulsified
formulation has the appearance of a milky-white solution. If
desired, the Gardner scale color index can be fairly accurately
translated to other color scale systems.
The fabric softeners of the invention generally comprise the
reaction products of a purified C.sub.14 - C.sub.18 fatty acid
alkyl ester mixture, triethanolamine and a quaternizing reagent,
preferably dimethyl sulfate. The select fatty acid alkyl esters are
preferably a mixture of substantial amounts of methyl esters of
stearic, palmitic, myristic and oleic and may include minor amounts
of other fatty substances.
Through extensive studies, it has been found that care must be
utilized in selecting a particular fatty acid alkyl ester mixture
if one is to attain a clean light colored product, a functional
fabric softener and a product which exhibits excellent rewetting
and whiteness-retention (non-yellowing) properties. Crude or
insufficiently purified fatty acid alkyl esters, when reacted with
triethanolamine and a quaternizing agent, yield dark colored
products which are not appealing to consumers. A convenient test
for determining whether a select fatty acid alkyl ester mixture is
of suitable purity for use in synthesizing the softener of the
invention, is to briefly shake a sample of the select fatty esters
with a small amount of sodium methoxide methanol solution and
observe the resulting color. If the resulting solution turns
reddish-brown or brown within about 10 minutes at room temperature,
it indicates that the fatty esters contain minute amounts of matter
which will discolor the ultimately formed softener. On the other
hand, if the resultant solution remains water-white or pale yellow,
it indicates that the ester mixture is of sufficient purity and
that the ultimately formed softener will have a white color index
on the Gardner scale of about 1 to 2.
Attention is also directed to the fact that a select pure fatty
acid alkyl ester generally does not yield commercially acceptable
softener products. Studies were conducted on the reaction products
of substantially pure oleic methyl ester, triethanolamine and
dimethyl sulfate and such oleic-based products failed to exhibit
good fabric softening characteristics. Similar studies were
conducted on the reaction products of substantially pure stearic
methyl ester, triethanolamine and dimethyl sulfate and such
stearic-based products failed to exhibit good emulsification
characteristics. In contrast, the reaction product of a mixture of
C.sub.14 - C.sub.18 fatty acid methyl esters, triethanolamine and
dimethyl sulfate has good softening, outstanding
whiteness-retention, self-emulsification and excellent rewetting
properties, along with a light color, having an index on the
Gardner scale in the range of 1 to 2.
Once a fatty acid ester mixture of sufficient purity is obtained,
the softener is readily synthesized in the following manner. About
two moles of a select fatty acid ester mixture are mixed with about
1 mole of triethanolamine, along with a small amount of a
transesterification catalyst, such as sodium methoxide. The mixture
is reacted at about 75.degree. to 115.degree.C. for a period of
time to attain the amine ester. The amine ester is then mixed with
a mole equivalent of dimethyl sulfate (or other quaternizing
reagent) and reheated to about 70.degree. to 100.degree.C. for a
period of time to obtain a viscous quaternary ammonium methol
sulfate product, identified as N-methyl-N,N-di-(.beta.-C.sub.14 -
C.sub.18 -acyloxy ethyl), N-.beta.-hydroxy ethyl ammonium metho
sulfate. This active softener is then mixed with an inert vehicle,
such as isopropanol to form a softener base which may be later
combined with other additives and increased amounts of vehicle to
provide a domestic softener formulation. Such formulations are
milky-white and have extended shelf-life over a wide range of
temperatures.
A specific exemplary embodiment of a synthesis route for producing
a preferred embodiment of the active softener is set forth
below.
DEMONSTRATION A
A commercially available fatty acid methyl ester mixture, Stepan C
65-P (a purified C.sub.14 - C.sub.18 fatty acid methyl ester
mixture comprised of about 40% to 55% palmitic, about 30% to 40%
oleic, about 7% to 12% stearic, about 4% to 8% linoleic and about
1% to 4% myristic along with minor (less than 1%) amounts of other
fatty acid substances, available from the Stepan Chemical Company,
assignee of the instant application, was tested for purity by
placing a small sample thereof in a conventional test tube along
with a small amount of 25% methanolic solution of sodium methoxide
and vigorously shaken. The color of this solution remained light
for more than 10 minutes and was judged to have a color index on
the Gardner scale of about 1. From previous experience, this
demonstrated that Stepan C 65-P was of sufficient purity to produce
a clean light colored softener.
A 4-neck, 1-liter reaction flask fitted with a stirrer,
thermometer, nitrogen inlet and a vacuum distillation assembly was
charged with 500 grams (1.78 moles) of Stepan C 65-P, 133.2 grams
(0.893 moles) of triethanolamine and 8 grams (25% solution in
methanol) of a sodium methoxide solution. The mixture was stirred
and heated to 91.degree.-105.degree.C. under vacuum (28 inches of
Hg) and nitrogen flow (about 50 cc/min.) for about 1 hour and 45
minutes. Approximately 80 ml. of methyl alcohol was collected in a
trap under a dry-ice-acetone bath and about 579 grams of the amine
ester were obtained. The amine ester was light in color, with a
color index of the Gardner scale of about 1.
369 grams (0.56 moles) of this amine ester was then slowly reacted
with 71 grams (0.56 moles) of dimethyl sulfate for about 2 hours at
a temperature of about 97.degree.C. A viscous quaternary ammonium
metho sulfate product was obtained. This product was mixed with 145
grams of isopropanol at a temperature of about 79.degree.C. to form
a 75% by weight fabric softener base solution.
This base solution was of a light color characterized by a color
index on the Gardner scale of about 1 (read at 55.degree.C., 75%
solids in 25% isopropanol). The base solution was then diluted and
mixed with large amounts of water. The resultant emulsion was
milky-white and did not separate upon standing.
This aqueous softener formulation (i.e. containing about 8% by
weight active softener) was then compared for softening and
non-coloring characteristics against commercially available
softeners by treating identical fabrics laundered with identical
detergents in a select cycle laundering operation. White terry
cloth towel swatches were placed in a typical domestic washing
machine, along with a select amount of detergent, washed in a
conventional manner and then, during the rinse cycle, treated with
a softener. Each towel was subjected to this cycle a select number
of times, adding a fabric softener to the rinse cycle after each
washing. The towels were then removed, dried and evaluated for
softness and whiteness by a select panel. Each panel member was
individually required to list his preference in descending order of
whiteness and softness on each towel. Thereafter, the numerical
value assigned to each towel was compiled and tabulated so that a
towel which had the lowest number under a given characteristic
indicated that a majority of the panel members placed this towel
most often in first place. In other words, a low numerical value
indicates that a large percentage of the panel judged that towel to
be whiter or softer than other towels in the test. The average and
compiled results are tabulated below.
TABLE I
__________________________________________________________________________
A batch of towels was laundered with a typical Na.sub.2 CO.sub.3
built detergent (Sears Roebuck Laundry Detergent) for a select
number of cycles, adding softener to the rinse after each wash, and
were then judged for the characteristics noted. Whiteness Softness
Softener 1 cycle 5 cycles 10 cycles 1 cycle 5 cycles 10 cycles
__________________________________________________________________________
None 12 12 21 48 48 46 Nu-Soft.sup.1 27 45 37 35 32 35 Downy.sup.2
44 39 45 23 12 12 T-di-C65Q.sup.3 38 24 15 14 28 27
__________________________________________________________________________
TABLE II
__________________________________________________________________________
A batch of towels was laundered with a typical phosphate built
detergent (Tide) for a select number of cycles, adding softener to
the rinse after each wash. The towels were then evaluated by the
panel. Whiteness Softness Softener 1 cycle 5 cycles 10 cycles 1
cycle 5 cycles 10 cycles
__________________________________________________________________________
None 14 11 12 48 48 48 Nu-Soft.sup.1 45 48 48 19 25 34 T-di-C65Q 24
32 29 34 26 21
__________________________________________________________________________
.sup.1 "Nu-Soft" is a registered trademark of CPC International
Inc. for fabric softener containing about 8% to 9% solids in an
inert vehicle. The active softener is a quaternized ditallow
imidazoline. .sup.2 "Downy" is a registered trademark of Proctor
& Gamble Co. for a fabric softener comprised of about 6% to 7%
solids in an inert vehicle. The active softener base is dimethyl
ditallow ammonium chloride. .sup.3 "T-di-C65Q" is an 8% by weight
of N-methyl-N,N-di-(.beta.-C.sub.14 - C.sub.18 -acyloxy ethyl),
N-.beta.-hydroxy ethyl ammonium metho sulfate of the invention in
an aqueous-alcohol solution.
It will be noted that the preferred softener of the invention does
not yellow fabrics over prolonged usage and provides softening
action to treated fabrics at least as good as obtainable from
presently available softeners. Further, the softeners of the
invention are not adversely affected by carbonate built detergents
or by phosphate built detergents, where either anionics or
nonionics are utilized as the primary surface active agents.
To demonstrate the outstanding rewetting characteristics of the
softeners here disclosed, a swatch-sink test was utilized.
Generally this test comprises placing 2 .times. 2 inch swatches of
softener-treated toweling on the surface of distilled water and
timing, as with a stop watch, the amount of time required for each
swatch to absorb water and sink below the surface of the water.
Each swatch was subjected to a single wash cycle, adding a softener
at the rinse cycle, dried and then carefully placed in the
distilled water. The average of four determinations for each
softener was recorded and is tabulated below.
TABLE III ______________________________________ *Softness Time
______________________________________ T-di-C65Q.sup.3 1-2 minutes
Downy.sup.2 Over 48 hours Nu-Soft.sup.1 Over 48 hours
______________________________________ .sup.1,2,3 ibid *All of the
softeners used contained approximately equal amounts of a nonionic
wetting agent.
As indicated earlier, the softener of the invention, i.e. T-di-C65Q
does not require additions of nonionic wetting agents and in the
above tests nonionic wetting agents were included to facilitate a
direct comparison with known softener formulations containing
nonionic wetting agents.
The softeners of the invention may be formulated with various
additives which include perfumes, optical brighteners, nonionics,
viscosity control agents, and other like additives conventionally
included in domestic softener formulations.
Various changes and modifications to the above described
embodiments of the invention may be made without departing from the
spirit and scope thereof and it is intended that all matters
contained in the above description shall be interpreted as
illustrative and not as limiting.
* * * * *