Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
-- 1 --
The present invention generally relates to
liquid compositions useful in treating fabrics, and
particularly to liquid bleaching solutions having
stably suspended ultramarine blue therein
Backqround Art
.. . .
A variety of substantially water insoluble
particulates are known and useful in treating fabrics.
For example, particulate pigments, such as ultramarine
blue, are used to mask the undesirable yellow color of
fabrics following laundering. During laundering~ if the
pigment particles are sufficiently small and are dis-
persed in ~he laundry solution, then they become en-
lS trained in the fabrics. Thus~ for example, ultramarineblue particles can be used to mask the yellowed color of
the fabrics by partially compensa~ing for the absorption
of short wavelength blue.
Although addition of particulates in con-
junction with laundering additives is a convenient means
of treating fabrics, it has been difficult to suffi-
ciently stably suspend the particulates, particularly in
a strongly oxidizing environment such as hypochlorite
bleach, while retaining water dispersibility of the
solution.
U.S. Pat. No. 4,271,030, issued June 2, 1981,
inventors Brierley et al., discloses a liquid hypo-
chlorite bleach having a particulate pigment~ such as
ultramarine blue, which is said to be stably suspended in
the colnposition by means of a flocculant, such as calcium
soap flocs and amine oxides, filling at least 50~ of the
88~
volume of the composition; and, ~.S. Patent No
3,663,442, issued May 16, 197~, inventor Briggs, dis-
closes liquid bleaching compositions haviny a finely
particulate terpolymer which imparts opacity to the
compositions
However, prior known compositions with par
ticulates in aqueous solutions have posed sedimentation,
coagulation or stability problems or have not found
commercial acceptability as dual bleaching and bluing
compositions.
SummarY of the Invention
Accordinglyl it is an object of the present
invention to provide a simple and e~ficient method for
stably suspending substantially inert and water insoluble
particulate agents for treating fabrics in aqueous
solutions, particularly bleaching solutions, with the
solutions being readily dispersed during laundering to
provide both bleaching, as well as coloring or bluing, of
the fabrics treated
Additional objects, advantages, and novel fea-
tures of the invention will be set forth in part in the
description which follows, and in part will become
apparent to those skilled in the art on examination.
In one aspect of the present invention, a
composition useful for treating fabrics is provided which
comprises an aqueous solution, a particulate$ and a
polymer dispersed in the aqueous solution which forms a
matrix in which the particulate is entrapped. The
aqueous solution preferably has from about 1 wt. ~ to
about 10 wt. % of a hypochlorite salt, and the polymer is
preferably an oxidized polyethylene or a polyethylene-
acrylic acid copolymer.
1, 2~ii2
In another aspect of the present invention7 a
method for producing a bleaching and bluing composition
is provided which comprises the steps of admixing a
quantity of molten polymer with base, contacting the
molten polymer in the presence of an anionic or a nonionic
surfactant with an aqueous solution to form an emulsion,
dispersing a quantity of particulate ultramarine blue in
the emulsion, and adding a water soluble salt, such as
sodium hypochlorite, until the emulsion collapses ~ith
the polymer forming a matrix in which particles of
ultramarine blue are entrapped.
A preferred liquid composition of the invention
has sodium hypochlorite in an amount of from about 3.~
wt.~ to about 6.2 wt.%, an anionic or nonionic surfactant
in an amount of from about 0.02 wt.% to about 5 wt.%, a
polymer derived from oxidized polyethylene or poly-
ethylene-acrylic acid copolymer in an amount of from
about 0.4 wt.% to about 0.6 wt.%, and ultramarine blue
particles in an amount of from about 0.1 wt.~ to about 0.2
wt.%. The polymer stably suspends and disperses the
ultramarine blue particles in the liquid composition.
When the preferred composition is used, as by adding to
wash water, then the polymer ~eleases the ultramarine
blue particles, which deposit on clothing being washed to
mask undesirable yellowing following laundering.
Best Mode of CarrYinq Out the Invention
Broadly, the present invention provides liquid
compositions which include a dispersed polymer forming a
matrix in which substantially water insoluble particles
are en~rapped. The particles-are substantially evenly
distributed throughout the composition and are suspended
therein by means of the polymer.
i2
Suitable particulates for suspending in compo-
sitions of the peesent invention are substantially inert
in the liquid solution, and include various known
pigments. For exampl~e, suitable pigment include
aluminosilicates, such as the ultramarines tred, green,
violet and blue), zeolites, and simple metal oxides -
(such as titanium dioxide and chromium dioxide).
Particulates useful in the present invention
are substantially water insoluble and often have a higher
density than the aqueous solutions in which they are
desirably dispersed for fabric treatment. For example,
ultramarine blue has a density of 2.35 g/cc, and
ultramarine blue particles begin settling out of aqueous
solution within about four hours, even when the particles
are of very small size.
Particulate density, however, is not believed
to be a critical factor in the present inventionJ as the
inventive compositions do not follow Stokes' law. Thus,
particulates suitable for the present invention may have
densities which are either higher or lower than the liquid
solution. Particle size will generally be from about 0.5
to abou~ 50 microns, preferably from about 0.5 to about 2
microns. Compositions of the invention will typically
have relatively low viscosity (about 20 to about 60
centipoise, or 0.02 to 0.06 pascal second), and thus are
readily poured or dispensed for use. Preferred compo-
sitions have a pH of at least about ll, preferably a p~ of
at least about 12.5.
Suitable polymers for practice of the present
invention form a matrix which is dispersed in an aqueous
solution and which entraps the particulate. Preferred
polymers are oxidized polyethylenes and polyethylene-
acrylic acid copolymers, which have melting points in the
~2~ 5~
range o~ about 90C to about 120C.
oxidizea polyethylenes suitable for the
present invention may vary considerably in structure.
~ne suitable oxidi~ed polyethylene has the general
Eormula shown by Figure 1, below, where "R" may be
hydrogen or alkyl groups. The ether and ester
functionalities may be linear (as illustrated by Fig. 1)
or be intramolecularly bonded ring structures. The
oxidized polyethylenes typically have a molecular weight
of about ~00 to about 3000 and have acid numbers from
about 30 to about 120.
FIG~RE 1
HO C (C~2lC (~l'12)y (C~J2 );LII R
O O O
~herein the total of x, y and z is from about 35 to about
250.
preferred polyethylene-acrylic acid copolymer
acids are slightly branched polyethylene chains con-
taining no oxygen functionality other than carboxyl
geoups, and have the general structure illustrated by
Figure 2, below. Molecular weight is typically ~rom
about 500 to about 6000, and the copolymers have acid
numbers ~rom about 30 to about 70.
~288~
FIGURE 2
COOH
R~cH~c~ cH2cH~R2
wherein the total of x and y is from about 12 to about 195,
Rl may be methyl or carboxyl, and R2 may be methyl or
carboxyl.
Preparation of compositions in accordance with
the present invention includes forming an emulsion of
suitable polymer with an anionic or a nonionic
surfactant The emulsified polymer forms a discon-
tinuous, internal phase which is dispecsed in the
continuous, external aqueous phase.
Suitable anionic surfactants, or e,nulsifying
agents, include soaps (such as are produced from teacting
fatty acids with al~alis or amine compounds), sulfates,
sulfonates and phosphates. Suitable nonionic surfac-
tants include polyoxyethylene and polyoxypropylene deri-
vatives, fatty alkanol amides and fatty amine oxides.
The emulsion is preferably prepared by melting
the oxidized polyethylene or polyethylene acid copolymer
with a solution of the surfactant and with base, and then
~ 20 slowly adding boiling water to the melt. At emulsion
inversion point, the viscosity of the composition droQs
and additional boiling water may be added to ad]ust the
emulsion to a desired weight percent of total solids. A
~2~;~2
quantity of particulate agent is then dispersed into the
emulsion, preferably with the particulate being ln a
weight ratio with respect to the emulsified polymer of
from about 1:2 to about 1:8.
Saponification and/or neutralization of the
molten polymer is performed prior to formation of the
emulsion, preferably with elevated pressure. (The
oxidized polyethylene is both saponified and neutralized.
I'he polyethylene-acrylic acid copolymer is neturalized.)
Smooth addition of boiling water preceding the emulsion
inversion point provides a uniform dispersion. Cooling
of the emulsion to room temperature is preferably at a
rapid rate (by means, for example, of a cooling jacket on
the emulsion kettle).
Following preparation of a suitable emulsion,
the selected particulate is then admixed, preferably at a
~- mix rate of about 100 to 300 rpm, forming a simple,
physical mixture. A water soluble salt is added until
the emulsion collapses (due to increased ionic strength
of the solution). Addition of the water soluble salt is
preferably by slowly adding a hot (about 21C to about
38C) aqueous solution in which the salt is dissolved,
preferably at a mix rate of about 100 to 300 rpm. Further
- additions of the salt solution may be used following
collapse of the emulsion to adjust the final, inventive
composition to desired solids ranges, and additional
surfactant may be added if desired.
Suitable water soluble salts include sodium
carbonate, sodium sulfate, sodium chloride, sodium hypo-
- 30 chlorite, calcium hypochlorite, calcium chloride, mag-nesium sulfate, lithium hypochlorite, and aluminum sul-
fate. Particularly preferred is sodium hypochlorite.
It has been found that the salt should be slowly
~2~355~3
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.
added into the emulsion. Too rapid addition tends to
precipitate polymer in a curd-like form
The following experimental methods, materials
and results are described ~or purposes of illustrating
the present invention. HoweVer, other aspects, advan-
- tages and modifications within the scope of the invention
-- will be apparent to those skilled in the aet to which the
invention pertains.
. Experimental
Cardipol*LPO-25 (available from Bareco Co.) was
- ~ utilized in preparing embodiments of the invention in
- which the polymer was an oxidized polyethylene. Cardipol*
-~ was found to have a relatively low molecular weight, and
samples with a range of saponification numbers 52-91 mg
15 KOH/g and melting points 98-115C were used.
Polyethylene-acrylic acid copolymers ("A-C'~
polyethylenes available from Allied) were found to have
higher molecular weights with acid numbers ranging 40-120
mg KOH/g and melting points 92-108C.
The water soluble salt was provided by a liquid
hypochlorite bleach containing sodium hypochlorite, and
the surfactants chosen were stable to hypochlorite.
Aqueous solutions of sodium hypochlorite are inherently
basic, as sodium hypochlorite is the salt of a weak acid
(hypochlorous acid) and a strong base (sodium hydroxide).
Since it is well known that hypochlorite ion is stabili~ed
by basic solutions, conventional agueous hypochlorite
bleach usually incorporates small amounts of sodium
hydroxide or sodium carbonate, which adjust the solution
to a pH of about 10.5 to 12Ø Agueous hypochlorite
bleaches can also include additional components and be of
higher pH.
Exarnples I-VII illustrate suitable emulsions
*Trade Marks
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as precursors in making composition~ in accordance with
the present invention, and examples VIII and IX illustrate
two preferred embodi~entsO
EXA~P~3 I
Into a 1 liter three-neck fla~k equipped with condensor
and mechanical stirrer was placed lOOg Cardipol* LPO-25,
83g sodium lauryl sulfate (30% active solution) and 6.8g
NaOH for saponification and neutralization. The mixture
was stirred and heated on an oil bath at 120 C until the
polymer was melted and homogeneous. Boiling water was
added in small portions (about 25ml) with rapid stirring
until there was a drop in viscosity. Additional hot water
was added to bring the volume to 500 ml. The emulsion was
allowed to cool to room temperature with stirring,
filtered through a cheese clotA and stored.
Preferred ranges for the emulsion are:
% Total solids 22-25%
; pH 11.5-12.-0
Viscosity 20 cps (Brookfield, 25 C)
Coagulum less than about 3
EXAMPLE II
Three compositions ~with ~arying amounts of an
anionic surfactant) were prepared in a manner analogous to
the preparation of Example I. Component weight
percentages of the three emulsions were as follows.
Components (a)wt.% ~b~t.~ (c)wt.%
Polymer (oxidized
polyethylene) 20 20 20
NaOH ~ 2 2
Sodium dodecyl diphenyl-
oxide disulfonate*
~45~ soln.) 1.1 6.6 11.1
Water 75.9 70.4 65.9
Dowfax* 2Al, available from DOW Chemical Co.
* Trade-mark
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.
- 10 ~ 5i52
EXAMPLE III
Another three emulsion compositions were
prepared having the component weight percentages as
follows.
Components~aLwt.% ~b2wt ~ (c)wt.
Polymer (oxidized
polyethylene) ~0 2Q 20
NaOH 2 2 2
Sodium lauryl sulfate*
(30% soln.) 10 lS.6 33.3
Water 67 60.4 43.7
Equex* S, available from Procter ~ Gamble
EXANPLE IV
- 15 Similarly, two compositions having different
ranges of a surfactant were prepared with the emulsion
components as follows.
Components (a)wt ~ (b)wt.
Polymer (oxidized
polyethylene) 20 20
NaO~ 2 2
Naphthalene sulfonate*
(50% soln.) 6 10
Water 72 6
Petro AG* Special, Petrochemical~ Co.
EXAMPLE V
In an analogous manner, another emulsion was
prepared with lauric acid as surfactant and having the
following weight percentages.
Components t.%
Polymer (oxidized
polyethylene) 20
NaOH 3
Lauric acid 3
Water 74
* Trade-mark
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35'i2
EX~MPLE VI
Another emulsion (with a nonionic surfac~.ant)
was prepared having the component weight percentages a~
follows.
Components wt.
Polymer (oxidi2ed
polyethylene) 20
NaOH 5
Linear, primary alcohol
ethoxylate (C12-C~5)* 73
~: Neodol* 25-3S, available from Shell Chemical
In a manner similar to emulsiPication of
~: oxidized polyethylenes (as in Example I), stable
emulsions utilizing polyethylene-acrylic acid copolymers
were prepared from neutralized A-C580 polymer with
equivalents of NaOH (1.3mgNaOH/g A-C580) added for
: neutralization. Examples VII and VIII characterize
/
/
*Trade-mark
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.. . .
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35~5~ :
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; emulsions with neutralized polyethylene acrylic acid
copolymer and t~o different surfactants.
EXAMPLE VII
Wt.% polymer Wt.% Suefactant Wt.~ Total Solids pH
510 3i3 11.8 12,1
10 8.3 13.4 11.8
10 16.6 16.1 12.1
10 33.3 22.0 11.2
sodium lauryl su1fate (30~ solution)
~t.% polymer Wt.% Surfactant Wt.% Total Solids pH
10 2.2 12,7 12.0
10 5.5 12.6 11.8
10 22.2 21.1 11.8
sodium dodecyl diphenyloxide disulfonate (45~ solution)
15EXAMPLE_VIII
Ultramarine blue particles were dispersed with
an oxidized polyethylene and sodium lauryl sulfate
emulsion in the following manner. An emulsion (as in
Example III, but with 5 wt.% surfactant) was used as the
dispersing agent. To lg ultramarine blue in 31g of water
was added 28g of the emulsion. Liqu~id hypochlorite
bleach (having 0.2 wt.~ NaOH and 3 wt.~ cocobetaine, 30~
solution, Lonzaine*12C, available from Lonza) was then
slowly added to a total amount of 940g with stirring. The
polymer emulsion collapsed upon aodition of the sodium
hypochlorite solution, and the ultrarnarine blue was
dispersed in the polymer matrix formed. The resulting
*Trade Mark
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composition was as follows:
Component Wt.%
~ltramarine blue 0.10
oxidized polyethylene 0.56
5 Sodium Lauryl sulfate 0.14
Cocobetaine 0.10
Sodium Hypochlorite 5,50
Water Remainder
EXAMPLE IX
10 ultramarine blue particles were dispersed with
a polyethylene-acrylic acid copolymer and sodium dodecyl
diphenyloxide disulfonate emulsion in the followiny
manner. An emulsion (as in Example VII but with 1.8 wt. %
sodium dodecyl diphenyloxide disulfonate) was used as the
lS dispersing agent. To 2~3.5g of ~his emulsion was added
0.5g of ultramarine blue in 15ml water. Then 4569 liquid
hypochlorite bleach containing 0.2 wt.% NaOH was slowly
added. Mild stirring during the addition produced a
composition in accordance with the present invention
which was stable at room temperature and at 37.8C. The
resulting composition was as follows-
Components Wt.~
Ultramarine Blue 0.10
polyethylene Acrylic Acid
copolymef 0.57
sodium dodecyl
diphenyloxide disulfonate 0.10
NaOH 0.20
NaOCl 5.50
30 Water Remainder
- 14 -
This composition, which is a particularly peeferred
embodiment, had a pH of about 12.5-12.6.
While the invention has been described in
connection with specific embodiments thereof, it will be
understood that it is capable of further modification,
and this application is intended to cover any variations,
uses or adaptations of the invention following, in
general, the principles of the invention and including
such departures from the disclosure as come within the
known or customary practice in the art to which the
. invention pertains and as may be applied to the essential
features hereinbefore set forth, and as fall within the
scope of the invention and the limits of the appended
claims .
