U.S. patent number 3,635,667 [Application Number 05/057,817] was granted by the patent office on 1972-01-18 for drycleaning with hydrogen peroxide.
This patent grant is currently assigned to FMC Corporation. Invention is credited to Harry M. Castrantas, Robert E. Keay, Donald G. MacKellar.
United States Patent |
3,635,667 |
Keay , et al. |
January 18, 1972 |
DRYCLEANING WITH HYDROGEN PEROXIDE
Abstract
Drycleaning of white garments is carried out by including, in
conventional solvent-detergent baths, hydrogen peroxide, water, and
sufficient volatile alkali (e.g. ammonia) to make the water phase
slightly alkaline, using limiting ratios of the ingredients to
insure adequate bleaching without damage to the fabric.
Inventors: |
Keay; Robert E. (Hightstown,
NJ), Castrantas; Harry M. (Trenton, NJ), MacKellar;
Donald G. (Yardley, PA) |
Assignee: |
FMC Corporation (New York,
NY)
|
Family
ID: |
27369336 |
Appl.
No.: |
05/057,817 |
Filed: |
July 23, 1970 |
Current U.S.
Class: |
8/142; 510/286;
8/101; 8/111; 510/304; 510/291; 510/435; 510/499; 510/373;
510/309 |
Current CPC
Class: |
D06L
4/12 (20170101); D06L 4/17 (20170101); D06L
1/04 (20130101) |
Current International
Class: |
D06L
1/00 (20060101); D06L 3/02 (20060101); D06L
3/00 (20060101); D06L 1/04 (20060101); D06l
001/00 () |
Field of
Search: |
;8/111,101,142
;252/103 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weinblatt; Mayer
Claims
We claim:
1. In the cleaning of textile fabrics in which they are treated
with at least five times their weight of a fat solvent containing a
small quantity of surfactant for a short period of time to remove
dirt and stains, the improvement which comprises adding to the bath
(a) from 0.25 to 2.5 percent weight of fabric of hydrogen peroxide;
(b) between 1.0 and 15 percent weight of fabric of water, using at
least twice as much water as hydrogen peroxide; (c) at least 2.0
percent weight of fabric of water plus peroxide; and (d) sufficient
volatile water-soluble alkali to bring the pH of the water phase to
at least 7.0.
2. The method of claim 1, in which the hydrogen peroxide content is
between 0.5 and 1.5 percent, the water is between 2.0 and 10.0
percent, and the aqueous alkali is sufficient to bring the pH to
8.5.
3. The method of claim 1, in which the aqueous alkali is ammonium
hydroxide.
Description
BACKGROUND OF THE INVENTION
For cleaning garments and other articles, two standard methods are
in general use-- washing with detergents in water, and drycleaning
with detergents in an oil solvent such as petroleum distillate or,
more recently, in a halogenated solvent such as trichloroethylene,
perchloroethylene or trichlorotrifluorethane. Drycleaning is more
expensive and difficult, and is generally restricted to cleaning
where the particular textiles involved are susceptible to damage by
washing in water, or where oil-soluble stains must be removed.
Typically, a modern drycleaning bath contains about 0.5 to 5.0
percent of a suitable detergent, and a very low level of water--
usually about 0.02 to 1.12 percent dispersed in a petroleum
distillate, perchloroethylene or other highly halogenated solvent.
About five times as much solvent bath is used as weight of fabric
to insure proper cleaning; more is advantageous, but of course adds
to the cost. Cleaning is generally carried out at room temperature,
and for times of the order of 20 minutes or less, for economic
reasons. Oil solubilization by the solvent, and dispersion of other
soil by the water and detergent, result in pickup of moisture and
dirt from the fabrics being cleaned. The insoluble dirt and most of
the excess moisture are removed by filtration, and the bath can be
reused several times. When the filtered bath becomes too dirty from
soluble dirt, it is distilled to produce clean solvent, which is
again reformulated into a cleaning bath by adding water and
detergent.
One of the major problems in drycleaning is that it is relatively
ineffective with white and light-colored garments, particularly
those containing cotton, linen or rayon, alone or blended with
synthetics. In conventional washing, use is made of chlorine or
peroxygen bleaches, so that the tendency to yellowing induced by
the washing operation is corrected by the bleach. The bleaches tend
to degrade cellulose somewhat, but careful control produces
effective washing and bleaching while holding the degradation
within acceptable limits. In drycleaning, on the contrary, no
bleaching is ordinarily carried out, and white fabrics tend to
yellow markedly when compared with whites which have been bleach
laundered.
The art has recognized the problem, and attempts have been made to
introduce bleaches-- particularly volatile bleaches such as
hydrogen peroxide into the drycleaning system. However, none of the
attempts has been really successful. The principal problem has been
that the art has been unable to bleach with hydrogen peroxide in
drycleaning systems without producing undue degradation of
cellulose. Because drycleaning is essentially a room temperature
operation, and contact times are short-- typically 15 to 20
minutes-- rather high bleach concentration is necessary, while
excessive fabric degradation occurs at hydrogen peroxide
concentrations well under those necessary for bleaching.
STATEMENT OF THE INVENTION
We have discovered that, despite the experience of the art, it is
indeed possible to get acceptable whitening of white fabrics,
approaching and equaling that of typical laundering with bleach,
without damage to the fabric, in drycleaning operations employing a
solvent and detergent, by using hydrogen peroxide, water and a
volatile alkali in controlled proportion relative to the weight of
fabric being cleaned (expressed as percent w.o.f.). To get these
results, it is essential to use in the drycleaning bath between
about 0.25 and 2.5percent w.o.f. of hydrogen peroxide, most
preferably 0.5 to 1.5 percent and preferably 2.0 to 10.0 percent
w.o.f. of water, using at least twice as much water as hydrogen
peroxide; at least 2.0 percent w.o.f. of water plus peroxide; and
sufficient volatile water-soluble alkali to bring the aqueous phase
to a pH of preferably 8.5 and at least 7.0, generally equivalent to
about 0.004 to 0.025 percent w.o.f. of 100 percent NH.sub.4 OH.
Within these limits, reasonably good bleaching is obtained,
approaching or equaling that of commercial laundering within the
preferred limits, and with less damage to the cellulosic fabrics
being cleaned than obtained in typical launderings.
DETAILED DESCRIPTION OF THE INVENTION
In the practice of the present invention, we start with
conventional dry cleaning baths consisting of a petroleum
distillate, or a halogenated solvent and a detergent. We have
worked with stoddard solvent, trichloroethylene, perchloroethylene
and trichlorotrifluoroethane, with similar results. Any detergent
which is soluble in the solvent and does not react with hydrogen
peroxide under the conditions of use is satisfactory. A wide range
of nonionic and anionic surfactants can be used.
Suitable anionics are alkylaryl sulfonates in which the alkyl
substituent varies from C.sub.8 through C.sub.18 carbon atoms and
in which the aryl substituent may be phenyl or naphthyl, such as
dodecylbenzene sodium sulfonate manufactured under the trademark
Santomerse; sodium alkyl sulfates in which the alkyl substituents
may vary from C.sub.8 through C.sub.18 carbon atoms, such as sodium
lauryl sulfate manufactured under the trademark Duponol P.C.; alkyl
sulfonates in which the alkyl substituent may vary from C.sub.8
through C.sub.18 carbon atoms such as sodium dodecyl sulfonate
manufactured under the trademark MP-189; aryl sulfonates in which
the aryl substituents may be phenyl or naphthyl such as sodium
tetrahydronaphthalene sulfonate sold under the trademark Alkanol S;
alkali metal salts of fatty acids having a carbon content of
C.sub.8 through C.sub.18 carbon atoms such as sodium stearate;
alkali metal lignosulfonates such as Polyfons, and phosphate esters
of long-chain alcohols.
Nonionics suitable for use include alkylphenyl-ethylene oxide
condensates in which the alkyl substituent may vary from C.sub.8
through C.sub.18 carbon atoms and the number of moles of condensed
ethylene oxide units varies from 1 to 100 per mole of alkyl such as
isooctylphenyl polyethoxy ethanol sold under the trademark Triton X
or dodecylphenyl polyethylene glycol ether sold under the trademark
Tergitol 12 P 12 ; polyoxyethylene thioethers such as STEROX SK;
propylene oxide-ethylene oxide condensates such as Pluronics
described in U.S. Pat. No. 2,674,619; fatty acid alkanolamides in
which the fatty acid constituent may vary from C.sub.8 through
C.sub.18 carbon atoms, such as lauric acid alkanolamide; alkyl
poly-(ethyleneoxy) ethanols in which the alkyl radical may vary
from C.sub.8 through C.sub.18 carbon atoms and the moles of
condensed ethylene oxide may vary from 1 to 100 per mole of alkyl
such as tridecyloxy poly-(ethyleneoxy) ethanol sold as Emulphogene
BC-840, or the ethylene oxide condensate of stearyl alcohol
containing about 10 moles of ethylene oxide per stearyl mole; and
the polyhydroxyalkyl fatty acid esters such as glycerol monooleate
or sorbitan stearate.
In a typical drycleaning bath, the solvent will contain 0.5 to 4.5
percent of the detergent, and a very small amount of water-- of the
order of about 0.02 to 0.12 percent-- i.e., a maximum of about 0.6
percent w.o.f. in a typical operation where 5 pounds of bath are
used per pound of fabric. For the practice of our invention, we use
much higher concentrations of water-- from 1.0 to 15 percent, and
for optimum results 2.0 to 10 percent w.o.f. With this, we combine
0.25 to 2.5 percent, most preferably 0.5 to 1.5 percent w.o.f., of
hydrogen peroxide, using at least twice as much water as peroxide.
Finally, it is essential to have present sufficient volatile alkali
to bring the aqueous phase to a pH of at least 7.0 and preferably
8.5, generally equivalent to 0.015 to 0.004 percent w.o.f. and
preferably to 0.024 to 0.001 percent of NH.sub.4 0.
Despite the relatively high concentration of hydrogen peroxide,
these compositions will bleach fabric without significant
deterioration of any cellulose contained therein. We believe this
is due to the initial dilution of the peroxide with at least twice
its weight of water, and the use of a volatile alkali to insure
rapid reaction when it encounters a reactive site.
We believe that the failure of the prior art in combining peroxide
with drycleaning baths has been due to the lack of realization that
cellulose fibers will selectively adsorb water and hydrogen
peroxide from drycleaning baths, so that the fabric is exposed not
to very dilute peroxide, as is the case in aqueous bleaching, but
to hydrogen peroxide in concentrations dependent only on the ratio
of hydrogen peroxide to the water in the system; if the common 50
percent peroxide of commerce is added to the bath, it is 50 percent
which is present on the fabric, and which acts on it.
To minimize this action, we use at least twice as much water as
hydrogen peroxide in the bath, and sufficient volatile alkali to
make the aqueous phase at least neutral, and preferably alkaline,
so that the peroxide acts far more rapidly than when on the acid
side. Since the pickup is not immediate, the fabric is in contact
with at most 33 percent peroxide for a very brief period-- the loss
of active oxygen in the bleaching action increases the amount of
water, so that the peroxide becomes more and more dilute on the
fabric during the operation; hence, fabric damage is minimized.
This is borne out by a series of tests run on swatches of cotton,
and 65/35 polyester/cotton blends, using perchloroethylene
containing 4 percent of an anionic detergent in a ratio of 15 parts
by weight of solvent to 1 fabric. Tea-stained swatches are used, of
the sort used in bleaching tests in aqueous wash systems to test
bleaches, where a single wash with a good active oxygen bleach will
give about 40 to 50 percent stain removal; fabric degradation was
measured by AATC method 82-1961, with results measured in fluidity
expressed as rhes, higher numbers expressing greater degradation.
The results are shown in the following table: ##SPC1##
The results show that even at low concentrations of peroxide,
insufficient to do any substantial bleaching, fabric damage is
nonetheless marked. At fairly high concentrations, there is some
bleach effect-- much below that of normal bleach laundering-- but
fabric damage is still objectionable. Mere dilution of the peroxide
gets somewhat improved bleach, still with more fabric damage than
is desirable. But by inducing rapid bleach with volatile alkali,
without increasing peroxide levels, we obtain both reduction in
fabric damage to below that of a typical laundering, and bleach
effectiveness approaching that of a typical laundering
operation.
The amounts of hydrogen peroxide which are used in accordance with
this invention depend on the degree of bleach desired; at least
about 0.25 percent w.o.f. is necessary if any really substantial
bleach effect is to be obtained. From about 0.5 to 1.5 percent
w.o.f. of hydrogen peroxide will give fair to good bleaching
without unacceptable cellulose degradation. Somewhat better
bleaching, with some but not excessive cellulose degradation, is
obtained between 1.5 and 2.5 percent w.o.f. of peroxide; Above
about 2.5 percent, cellulose degradation is, in our opinion,
excessive. We prefer, therefore, to operate in the range of about
0.5 to 1.5 percent of peroxide.
We use at least 2 parts by weight of water per part of peroxide,
using about 1.0 to 15 percent w.o.f., and preferably 2 to 10
percent w.o.f. Water plus peroxide should equal 2 percent w.o.f.,
or effective bleaching is not obtained; we believe this is due to
the problem of effective distribution of bleach over the
fabric.
With higher w.o.f. concentrations of water and peroxide larger
ratios of bath to fabric than the ordinary minimum of 5 to 1 are
desirable, since otherwise the bath may be unable to effectively
keep the aqueous system properly dispersed.
The use of sufficient alkali to render the aqueous phase at lease
neutral is essential for our desirable results, and preferably
enough alkali is added to make the aqueous phase alkaline. Since
hydrogen peroxide in water is acid, with pH depending on
concentration, the amounts added will vary somewhat. Generally, we
use from about 0.004 to 0.020 percent w.o.f. of NH.sub.4 OH (100
percent basis) or equivalent in other volatile alkali. While
ammonium hydroxide is the cheapest and most readily available
volatile alkali, we have successfully used various water-soluble
volatile lower mono-, di-, and tri-alkyl amines. Water solubility
and volatility are essential characteristics; unobjectionable odor
is a desirable property, which many amines lack.
SPECIFIC EXAMPLES OF THE INVENTION
The following specific examples of the invention are given by way
of illustration and not by way of limitation.
EXAMPLE 1
A 100 -pound load of naturally soiled garments was composed of
50/50 by weight of colored and white shirts and colored slacks in
both 65/35 Dacron/cotton blends and 100 percent cotton. The
drycleaning bath contained 500 pounds of solvent, in this case
perchloroethylene, 4 pounds of detergent, in this case the
isopropylamine salt of dodecylbenzene sulfonate, 2 pounds of 50
weight percent of aqueous hydrogen peroxide and 1 pound of 2.0
weight percent of aqueous NH.sub.4 OH.
The soiled garments were cleaned for a period of 15 minutes in a
typical drycleaning machine and then forced hot air dried.
These garments were noticeably cleaner and colors brighter than
comparable garments cleaned under similar drycleaning conditions
but without the combination of hydrogen peroxide, water, and
NH.sub.4 OH.
EXAMPLE 2
In this example, the conditions of testing were the same as those
of example 1 except that 4 pounds of the sodium salt of a
monophosphate ester of 1-dodecanol was used as the detergent in
place of the isopropyl amine salt of dodecylbenzene sulfonate.
The garments cleaned in this example were also cleaner and brighter
than those cleaned via conventional techniques.
EXAMPLE 3
In this example, the conditions of testing were the same as those
of example 1 except that 500 pounds of stoddard solvent (saturated
hydrocarbons) was used in place of perchloroethylene as the
solvent.
The garments cleaned in this example again exhibited a cleaner,
brighter appearance than those cleaned in a similar system but
without hydrogen peroxide, water, and NH.sub.4 OH.
EXAMPLE 4
In this example, the conditions of testing were the same as those
of example 1 except that 1 pound of 0.5 weight percent of aqueous
NH.sub.4 OH was used in place of 1 pound of 2.0 weight percent of
aqueous NH.sub.4 OH.
The garments of this example were of slightly poorer quality than
those of example 1, but still superior to those cleaned via
conventional practice.
EXAMPLE 5
In this example, the conditions of testing were the same as those
of example 1 except that 5 pounds of water was added in addition to
the other specified components.
The garments of this example were of approximately the same quality
(cleanliness and brightness) as those of example 1, but noticeably
cleaner than those cleaned in the absence of hydrogen peroxide,
water, and NH.sub.4 OH.
In these examples, it was impossible to assess fabric damage, but
none of the garments were damaged by the operation.
Obviously, examples could be multiplied without departing from the
scope of the invention as defined in the claims.
* * * * *