U.S. patent number 3,904,359 [Application Number 05/286,995] was granted by the patent office on 1975-09-09 for post-wash fabric treating method.
This patent grant is currently assigned to Colgate-Palmolive Company. Invention is credited to Pallassana Ramachandran.
United States Patent |
3,904,359 |
Ramachandran |
September 9, 1975 |
Post-wash fabric treating method
Abstract
A fabric treating composition for use in preventing the staining
of fabrics consisting essentially of an aqueous solution of a
complexing acid and a cationic fabric softening agent, the
complexing acid and the softening agent being present in amounts so
that on dilution with water the complexing acid comprises from 0.01
to 0.1% by weight of the dilution and the softening agent comprises
from 0 to 0.1% of the dilution.
Inventors: |
Ramachandran; Pallassana
(Robinsville, NJ) |
Assignee: |
Colgate-Palmolive Company (New
York, NY)
|
Family
ID: |
26964195 |
Appl.
No.: |
05/286,995 |
Filed: |
September 7, 1972 |
Current U.S.
Class: |
8/137; 8/139;
510/524; 510/522 |
Current CPC
Class: |
D06F
35/006 (20130101); C11D 3/2075 (20130101); D06M
13/35 (20130101); D06M 13/203 (20130101); D06M
13/46 (20130101); D06M 13/192 (20130101); C11D
3/0015 (20130101); Y10T 442/2352 (20150401); Y10T
442/2279 (20150401) |
Current International
Class: |
C11D
3/00 (20060101); D06F 35/00 (20060101); D06M
13/192 (20060101); D06M 13/00 (20060101); D06M
13/46 (20060101); D06M 13/35 (20060101); D06M
13/203 (20060101); C11D 3/20 (20060101); B08B
003/00 () |
Field of
Search: |
;252/8.6,8.8,142
;8/137,139 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lechert, Jr.; Stephen J.
Attorney, Agent or Firm: Baron; S. J. Sylvester; H. S.
Blumenkoph; N. M.
Claims
What is claimed is:
1. A process for treating fabrics which are subject to yellowing in
rinse water comprising laundering said fabrics and treating said
fabrics at a temperature of about 70.degree.F to about 120.degree.F
with an aqueous solution containing from about 0.01 to about 0.1%
by weight of a complexing acid and from 0 to 0.1% by weight of a
cationic fabric softener, whereby yellowing imparted to said
fabrics in part by said cationic fabric softener is substantially
reduced by said complexing acid.
2. The process of claim 1 wherein the ratio of said complexing acid
to said cationic softening agent is from 1:1 to 5:1.
3. The process of claim 1 wherein the ratio is approximately
2:1.
4. The process of claim 1 wherein said organic complexing acid is
selected from the group consisting of citric acid, maleic acid,
tartaric acid, fumaric acid, adipic acid, succinic acid and
mixtures thereof.
5. The process of claim 1 wherein said acid is citric acid.
6. The process of claim 1 wherein said cationic fabric softening
agent is N-tallow propylene diamine.
7. The process of claim 1 wherein said softener is included in an
amount of about 0.01 to about 0.03% by weight.
8. The process of claim 1 wherein said softener is selected from
the group consisting of cationic nitrogen containing compounds
containing 1 to 2 straight chained organic radicals of at least 8
carbon atoms and at least one chain containing about 12 to about 22
carbon atoms.
9. The process of claim 8 where said softener is a quaternary
ammonium compound of the formula ##SPC2##
wherein R.sub.1 is an aliphatic radical having about 8 to about 22
carbon atoms, R.sub.2 is an aliphatic radical having about 8 to
about 22 carbon atoms or an alkyl radical having about 1 to about 4
carbon atoms, R.sub.3 and R.sub.4 are lower alkyl radicals, n is a
number between about 1 and about 15 and X is a water soluble salt
forming anion.
Description
This invention relates to a post-washing treating composition and
method for using the same. More particularly, this invention
relates to a post-washing treating composition and method which
effectively prevents staining or yellowing of fabrics by metal
ions.
Although cationic fabric treating fabric softening agents have been
known and utilized since the early 1930's, the use of the cationic
fabric treating agents has decreased as compared to the nonionic
fabric softening agents since the cationic fabric softening agents
have a marked tendency to impart a yellowness to fabrics which are
continually treated with the same. Furthermore, the cationic fabric
softening agents can only be utilized in the rinse cycle since the
majority of commercially available detergents are of the anionic
type and are not compatible with these cationic fabric softening
agents. The cationic fabric softening agents, although less
preferred, are generally less expensive to utilize and,
accordingly, it would be desirable to be able to utilize such
cationic agents in the rinse cycle without causing the fabrics be
become yellowed.
In addition to yellowness imparted by cationic fabric softening
agents, the fabrics are often stained by metal cations present in
various soils, especially clay type soils. Up to now the only means
for treating these metal type stains was the removal of the stains
subsequent to their setting on the fabrics by way of bleaching and
repeated washing. Each of these treatments, of course, is not
completely satisfactory since continued bleaching of fabrics tends
to degrade the same and shortens their useful life. The continued
washing is not completely effective in removing the stains and
tends to impart a certain boardiness to the fabrics, thus
necessitating the use of a fabric softener.
Although complexing acids, such as citric acid, and the salts of
these acids have been recently employed as supplemental builders
for use in conjunction with various detergent compositions as
replacements for the phosphate and nitrilo type builders previously
employed, these materials have not been utilized in postwashing
fabric treating compositions, such as fabric softeners. Citric acid
and other complexing acids have found utility for a wide number of
uses ranging from a use as a wall paper paste remover to use as an
active ingredient in a detergent composition for removing fishy
type odors.
It is, therefore, within the above environment and disadvantages
that the composition and process of the present invention has been
developed. Briefly, the fabric treating composition of the present
invention which is for use in preventing the staining of fabrics
consists essentially of an aqueous solution of a complexing acid
selected from the group consisting of citric acid, maleic acid,
tartaric acid, fumaric acid, adipic acid, succinic acid and
mixtures thereof and a cationic fabric softening agent such that on
dilution with water the resulting composition contains from 0.01 to
0.1% by weight of complexing agent and from 0 to 0.1% by weight of
softening agent. The method of the present invention comprises a
method for preventing the yellowing or staining of fabrics
comprising treating a fabric in the rinse with an aqueous solution
consisting essentially of water, a complexing acid selected from
the group consisting of citric acid, maleic acid, tartaric acid,
fumaric acid, adipic acid, succinic acid and mixtures thereof and a
cationic fabric softener, the complexing acid and cationic fabric
softener being present in amounts sufficient to produce a
concentration of from about 0.01 to 0.10% by weight of the acid and
from about 0 to 0.10% by weight of the cationic fabric
softener.
It is, therefore, the primary object of the present invention to
provide a fabric treating composition which effectively prevents
yellowing and staining of fabrics.
It is a further object of the present invention to provide a method
for preventing the staining and yellowing of fabrics by rinsing the
fabrics in a solution consisting essentially of water, a complexing
acid and a cationic fabric softener.
It is a still further object of the present invention to provide a
method wherein the fabrics are treated so as to prevent the same
from being stained by the subsequent soiling with mineral
containing soils.
It is a still further object of the present invention to provide a
method for preventing fabrics from yellowing through the continued
use of a cationic fabric softening agent.
Still further objects and advantages of the composition and process
of the present invention will become more apparent from the
following, more detailed description thereof.
The composition of the present invention which obviates the above
disadvantages and which is for use in preventing the staining or
yellowing of fabrics consists essentially of an aqueous solution of
a complexing acid selected from a group consisting of citric acid,
maleic acid, tartaric acid, fumaric acid, adipic acid, succinic
acid and mixtures thereof, and a cationic fabric softening agent in
an amount sufficient to produce, upon dilution, a concentration of
from 0.01 to 0.1% by weight of complexing acid and 0 to 0.1% by
weight softening agent.
The process of the present invention comprises rinsing a fabric in
an aqueous solution consisting essentially of water, a complexing
acid and a cationic fabric softening agent wherein the cationic
fabric softening agent and the complexing acid are present in
amounts sufficient to produce a concentration of from 0.01% to
0.10% by weight of the complexing acid and from 0 to 0.10% by
weight of the cationic fabric softening agent.
The primary ingredient in the composition of the present invention
is the complexing acid which is selected from citric acid, maleic
acid, tartaric acid, fumaric acid, adipic acid, succinic acid and
mixtures thereof. The preferred acids are citric and tartaric acid
with citric being most preferred.
The complexing acid may be present in the final diluted rinse
solution in an amount ranging from 0.01 to 0.1% by weight and
preferably 0.02 to 0.05% by weight. Of course, it will be most
convenient to utilize a concentrated solution of the acid for
consumer convenience and packaging economies. Generally, since most
top loading washing machines have from 15 to 20 gallon capacity,
the concentrated form of the composition will generally comprise
from 2 to 25% by weight of acid in a water solution. The important
parameter is the dilution concentration so any concentrate
composition will be solely for convenience in use.
In use, a small amount of the complexing acid is deposited on the
fabric so as to provide active complexing sites for metal ions
contained in soils, etc. In essence, the present composition and
process are of a preventative nature since, by depositing a small
amount of acid on the fabric, future metal stains are virtually
eliminated. The same complexing acid also prevents the yellowing of
fabrics due to a build-up of cationic fabric softeners.
Fabric softeners must be strongly attracted to fabrics in order to
function properly; however, this attraction which is especially
strong in cationic softeners also causes softener buildup or
yellowing. The complexing acids, when used in conjunction with
cationic fabric softeners lessen the tendency to build-up without
interfering with their softening function.
Although in conventional compositions and processes, the salts of
these organic, complexing acids are often utilized with similar or
equivalent results, the sodium salts of the above noted acids as
well as the other alkaline and the alkaline earth salts do not have
the complexing properties necessary for the enhancement of the
removal of the soil from the fabric. Accordingly, in the process
and composition of the present invention, only the acids themselves
and not their salts may be utilized.
Furthermore, only the organic complexing acids aid in the removal
of these ions since the removal is not a function of pH as
demonstrated by the inability of mineral acid solutions to
effectively prevent staining from irremovable metal ions. Also,
these latter acids are too strong for continued use since they tend
to degrade the fibers.
The cationic fabric softening compounds useful in the composition
of the present invention generally comprise cationic nitrogen
containing compounds, such as quarternary ammonium compounds and
amines containing one or two straight chained organic radicals of
at least 8 carbon atoms and preferably containing at least one
straight chained organic radical containing from 12 to 22 carbon
atoms.
Generally, the quarternary ammonium softening agents have the
following formulas ##SPC1##
wherein R.sub.1 is a long chain aliphatic radical having from 8 to
22 carbon atoms, R.sub.2 is a long chained aliphatic radical having
from 8 to 22 carbon atoms or is a lower alkyl radical having from 1
to 4 carbon atoms, R.sub.3 and R.sub.4 are lower alkyl radicals, n
is a number between 1 and 15 and X is a water soluble salt forming
anion, such as a halide, i.e., chloride, bromide, iodide; a
sulfate, acetate, hydroxide, methasulfate or similar inorganic or
organic solubilizing mono- or dibasic radical. Examples of
quaternary ammonium softening agents suitable for use in the
composition of the present invention include the following:
hydrogenated ditallow dimethyl ammonium chloride, ethoxylated
distearyl dimethyl ammonium chloride,
1-hydroxyethyl-1-methyl-2-heptadecyl imidazolinium chloride;
dimethyl distearyl ammonium chloride; trimethyl stearyl ammonium
bromide; cetyl trimethyl ammonium chloride, di-coco dimethyl
ammonium chloride; cetyl pyridinium chloride; higher alkyl dimethyl
benzyl ammonium chloride; di-isobutyl phenoxy ethoxy ethyl dimethyl
benzyl ammonium chloride; lauryl isoquinolinium bromide; distearyl
dimethyl quarternary ammonium bromide; distearyl dimethyl
quaternary ammonium methylsulfate; dicoco dimethyl quaternary
ammonium chloride; dimethyl arachidyl, behenyl quaternary ammonium
chloride; di-(soya) dimethylammonium chloride, and di-(coco)
dimethylammonium chloride.
Examples of amines which may be utilized in the composition of the
present invention include primary tallow amine, primary coco amine,
primary halogenated tallow amine, n-tallow 1,3-propylene diamine,
oleyl 1,3-propylene diamine, and coco 1,3-propylene diamine.
The term "coco" when utilized refers to fatty acid groups formed in
coconut oil fatty acids. Such acids contain from about 8 to 18
carbon atoms per molecule predominating in the C.sub.12-14
acids.
Although the process and composition of the present invention are
operative without the use of the cationic softeners, it is a
preferred embodiment to utilize a mixture of the complexing acid
and softener in a solution. Generally, the softener comprises from
0 to 0.1% by weight of the rinse water subsequent to dilution and
preferably from 0.01 to 0.03% by weight. As with the acid, the
softener will have a similar concentration in the concentrate,
i.e., from 0 to 25% by weight.
Another important factor in the composition of the present
invention is the ratio by weight of the cationic agent to the
anti-yellowing agent, i.e., the complexing acid, since within
certain ratios the non-yellowing properties are most evident. This
ratio is generally from 1:1 to approximately 1:5 softener to acid
with optimum results being obtained at a ratio of approximately
1:2.
Furthermore, it has been found that the process of the present
invention is not basically temperature dependent and performs well
using cold and warm water rinse solutions. Also, the process can be
conducted using water of any reasonable degree of hardness
although, obviously, the use of softer rinse water is
preferred.
Since the composition of the present invention in use tends to
acidify the rinse water, a number of additional beneficial results
have been noted, namely permanent press resins tend to be more
stable ans calcium precipitants such as CaCO.sub.3 tend to be
removed leaving the fabrics with a better hand and feel.
The composition of the present invention will now be more fully
illustrated by way of the following specific examples which are for
the purpose of illustration only and are in no way to be considered
as limitive of the composition of the present invention. In the
following examples, all parts and percentages are by weight and all
temperature in degrees farenheit.
Example 1 and Comparative Examples 1 and 2
Three series of identical 50/50 polyester cotton permanent press
swatches are soiled with a clay soil. These soiled swatches are
then washed with a detergent as a 1.5 g/liter concentration using a
water having a hardness of 150 ppm. The detergent composition is
10% tridecylbenzene sulfonate, 2% C.sub.14-15 etoxylated (11EO)
alcohol, 1% sodium soap, 33% sodium carbonate, and 7% sodium
silicate. These series or sets of swatches are then rinsed with the
following rinse composition as set forth in Table I. The swatches
are then soiled, washed and rinsed in this manner four additional
times. The reflectance (Rd values) after the first and fifth wash
are shown below with a higher Rd value indicating increased
whiteness.
TABLE I ______________________________________ Rd After Rd After
Example No. Rinse 1st Wash 5th Wash
______________________________________ Comp. Ex. 1 Water (150ppm)
75.5 59.7 Comp. Ex. 2 HCl + Water 76.9 62.3 pH = 4 Example 1 0.02%
Citric Acid in Water 77.8 67.8 pH = 4
______________________________________
As is evident from Table I, the utilization of citric acid produces
an increased whiteness from the first wash through the fifth wash
with the whiteness becoming more apparent after a greater number of
washings. Since the citric acid and hydrochloric acid rinses both
have the same pH, this shows that the increased whiteness obtained
is not a function merely of pH but can be obtained only utilizing
an organic complexing acid, such as citric acid. In each of the
above noted rinse solutions, the water which is utilized has a
hardness of 150 ppm.
Example 2
Utilizing the procedure of Example 1, the citric acid rinse is
replaced by the following organic complexing acid rinse solutions:
(A) 0.01% tartaric acid; (B) 0.05% maleic acid; (C) 0.1% fumaric
acid; (D) 0.02% adipic acid; (E) 0.06% of a 50/50 mixture of maleic
acid and citric acid; and (F) 0.08% citric acid.
When compared to a similar swatch of fabric rinsed only in plain
water of a similar hardness, the swatches rinsed in the above acid
solutions show increased whiteness. This increased whiteness is
evident from the first wash and the whiteness differential
increases with every subsequent wash.
Comparative Example 3
In order to show the inoperability of the alkali metal salts of the
organic complexing acids utilized in the composition of the present
invention, the procedure of Example 1 is repeated with the
exception that the following salt solutions are utilized as the
rinse solution: (A) 0.01% of the sodium salt of tartaric acid; (B)
0.05% of the potassium salt of maleic acid; (C) 0.1% of the
ammonium salt of fumaric acid; (D) 0.02% of the sodium salt of
adipic acid; (E) 0.06% of the sodium salts of a 50/50 mixture of
maleic acid and citric acid; and (F) 0.08% of the sodium salt of
citric acid.
When the swatches rinsed in each of the above solutions are
compared both with similar swatches using a plain water rinse and
with the swatches of Example 2, the difference in whiteness and
feel of the swatches is immediately apparent with the whiteness of
the swatches rinsed in accordance with Example 2 being whiter than
the corresponding swatches rinsed in accordance with Comp. Ex.
3.
Example 3 and Comparative Example 4
Two sets of cotton terry towel swatches are rinsed three times
utilizing the rinse solutions as shown in Table II.
TABLE II ______________________________________ Example No. Rinse
Rd Value "b" value ______________________________________ Comp. Ex.
4 0.01% solution of 74.9 4.0 N-tallow propylene diamine Example 3
0.01% N-tallow pro- 82.5 2.7 pylene diamine + 0.02% citric acid
______________________________________
The above rinse solutions are conducted at a temperature of
approximately 120.degree.F. which corresponds to a normal warm
water rinse. In Table II, the Rd value is the whiteness with higher
values indicating increased whiteness and the b values indicate
yellowness with higher values indicating increased yellowness. As
is immediately apparent, the terry towel swatches which are rinsed
in the diamine + citric acid show improved results over those
rinsed in just the diamine alone. Furthermore, the softening of
each set of swatches is approximately equal.
Example 4 and Comparative Example 5
The procedure of Example 3 and Comp. Example 4 is repeated with the
exception that the rinse solutions are maintained at a temperature
of 70.degree.F, i.e. a cold water rinse. The results are shown in
Table III.
TABLE III ______________________________________ Example No. Rinse
Rd Value "b"Value ______________________________________ Comp. Ex.
5 0.01% solution of 75.6 4.4 N-tallow propylene diamine Example 4
0.01% N-tallow 81.3 3.5 propylene diamine - 0.02% citric acid
______________________________________
Again, the diamine + citric acid produces superior results when
compared to the diamine alone. This indicates that the temperature
of the rinse water has little, if any, effect on the decreased
yellowness and increased whiteness of the composition of the
present invention.
Example 5
The procedure of Example 3 is repeated with the exception that the
following cationic fabric softener and organic acid rinses are
utilized: (A) 0.1% 1-hydroxyethyl-1-methyl-2-heptadecyl
imidazolinium chloride and 0.1% citric acid; (B) 0.01% dimethyl
distearyl ammonium chloride and 0.05% maleic acid; (C) 0.04%
trimethyl stearyl ammonium bromide and 0.08% tartaric acid; (D)
0.03% lauryl isoquinolinium bromide and 0.10% succinic acid; (E)
0.05% oleyl 1,3-propylene diamine and 0.1% fumaric acid; and (F)
0.2% primary tallow amine and 0.1% of a 50/50 mixture of citric
acid and adipic acid.
Each of the above compositions when compared to a rinse composition
utilizing only the cationic softening agent has increased whiteness
and decreased yellowness with no apparent differentiation in degree
of softening.
As is apparent by way of the foregoing examples which are for the
purposes of illustration only, the composition and process of the
present invention provide a rinse cycle treatment composition and
process which reduces the yellowing caused by cationic softening
agents and increases whiteness.
* * * * *