Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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ABRASION RESISTANT POLYMERIC FOAM
AND STAIN RECEIVERS MADE THEREFROM
FIELD OF THE nVVENTION
The present invention relates to an improved foam stain receiver that is used
to spot-clean
fabrics and that is abrasion resistant.
BACKGROUND OF THE INVENTION
Fabric cleaning and refreshment processes such as laundering and dry cleaning
operations
typically are used to clean entire garments. However, in some circumstances
the user wishes only
to clean localized areas of fabrics. Alternatively, the user may wish to spot-
clean localized areas
of stain before subjecting the entire fabric garment to an overall dry
cleaning or laundering
operation.
It has been deternuned that certain absorbent polymeric foam materials are
especially
useful in spot cleaning operations. These polymeric foams are prepared from
High Intennal Phase
_Emulsions (hereafter referred to as "HIPEs"). See, for example, U.S. Patent
No. 5,260,345
(DesMarais et al.) issued November 9, 1993, U.S. Patent No. 5,268,224
(DesMarais et al.) issued
December 7, 1993, DYER '207 and DESMARAIS '222 (each of which is incorporated
herein by
reference), which generally describe HIPE-derived polymeric foams. In a
typical operation, the
polymeric foam functions as a "stain receiver" by drawing the liquid cleaning
composition through
the stained/spotted area of the fabric. Thus, the stain/spot material which
has been mobilized by
the cleaning composition is captured in the polymeric foam. Importantly, the
polymeric foam
minimizes the tendency of the stain/spot to spread laterally on the fabric,
thereby minimizing the
formation of "rings" on the fabric.
In a preferred spot cleaning operation, a polymeric foam stain receiver is
positioned
beneath a stained area of fabric. A cleaning composition is then applied to
the stain and worked
into the stain by mechanical action. Such mechanical action preferably
comprises using
compressional, mainly Z-directional force in the manner disclosed herein. It
has now been
determined that previously described polymeric foam, when used as the stain
receiver, may not be
sufficiently robust to withstand vigorous forces encountered during the
cleaning operation. Simply
stated, the polymeric stain receiver may be sufficiently friable under
mechanical force that it may
begin to disintegrate, with the result that the polymeric foam flakes off.
This results in a messy
appearance in the area where the spot cleaning process is being conducted.
Moreover, the
polymeric foam flakes may be undesirably transferred to the fabric being spot-
cleaned.
One method of overcoming the problems associated with prior foam stain
receivers is
disclosed in U.S. Provisional Application No.60/053,191. This application is
directed to a
polymeric foam stain receiver enrobed in a coversheet. While this method of
protecting the
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polymeric foam is effective, it adds costs and processing steps to the
manufacturing of stain
receivers. Hence, there is a continuing need for improved polymeric foam stain
receivers that
resist abrasion whereby they do not flake or disintegrate during use.
Having discovered the problems associated with polymeric foam when used in the
present
manner, the invention herein employs a new composition for the polymeric stain
receiver, thereby
minimizing such problems.
BACKGROUND ART
WO 97/00993A1, published January 9, 1997 to Welter, et al.; WO 97/00990A2,
published January 9, 1997 to Tyerech, et al.; GB 2,302,553A, published January
22, 1997 to
Telesca, et al.; GB 2,302,878A, published February 5, 1997 to Welter, et al.;
and GB 2,302,879A,
published February 5, 1997 to Sidoti, et al. all relate to in-dryer fabric
cleaning. U.S. 4,532,722,
issued to S. H. Sax, August 6, 1985, relates to a fabric conditioning device
for use in a laundry
dryer. A peracid-containing dry cleaning composition is described in U.S.
4,013,575, issued to H.
Castrantas, et al., March 22, 1977. Dry cleaning processes are disclosed in:
U.S. 5,547,476
issued 8/20/96 to Siklosi & Roetker; U.S. 5,591,236 issued 1/7/97 to Roetker;
U.S. 5,630,847
issued 5/20/97 to Roetker; U.S. 5,630,848 issued 5/20/97 to Young, et al.;
U.S. 5,632,780 issued
5/27/97 to Siklosi; EP 429,172A1, published 29.05.91, Leigh, et al.; and in
U.S. 5,238,587,
issued 8/24/93, Smith, et al. Other references relating to dry cleaning
compositions and processes,
as well as wrinkle treatments for fabrics, include: GB 1,598,911; and U.S.
Patents 4,126,563,
3,949,137, 3,593,544, 3,647,354; 3,432,253 and 1,747,324; and German
applications 2,021,561
and 2,460,239, 0,208,989 and 4,007,362. Cleaning/pre-spotting compositions and
methods are
also disclosed, for example, in U.S. Patents 5,102,573; 5,041,230; 4,909,962;
4,115,061;
4,886,615; 4,139,475; 4,849,257; 5,112,358; 4,659,496; 4,806,254; 5,213,624;
4,130,392; and
4,395,261. Sheet substrates for use in a laundry dryer are disclosed in
Canadian 1,005,204. U.S.
3,956,556 and 4,007,300 relate to perforated sheets for fabric conditioning in
a clothes dryer. U.S.
4,692,277 discloses the use of 1,2-octanediol in liquid cleaners. See also
U.S. Patents 3,591,510;
3,737,387; 3,764,544; 3,882,038; 3,907,496; 4,097,397; 4,102,824; 4,336,024;
4,594,362;
4,606,842; 4,758,641; 4,797,310; 4,802,997; 4,943,392; 4,966,724; 4,983,317;
5,004,557;
5,062,973; 5,080,822; 5,173,200; EP 0 213 500; EPO 261 718; G.B. 1,397,475; WO
91/09104;
WO 91/13145; WO 93/25654 and Hunt, D.G. and N.H. Moms, "PnB and DPnB Glycol
Ethers",
HAPPI, April 1989, pp. 78-82.
SUMMARY OF THE INVENTION
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The present invention encompasses a polymeric foam and an abrasion resistant
stain
receiver comprising polymeric foam, wherein the polymeric foam comprises a
polymerized water-
in-oil emulsion having:
1) an oil phase comprising:
a) from about 85 to about 98% by weight of a monomer component, said monomer
component comprising:
i) from about 25 to about 70% by weight of a substantially water-insoluble,
monofunctional monomer capable of forming a polymer having a Tg of about
25°C or less;
ii) from about 25 to about 65% by weight of a substantially water-insoluble,
monofunctional comonomer capable of imparting toughness about equivalent to
that provided by styrene;
iii) from about 5 to about 25% by weight of a first substantially water-
insoluble, polyfunctional crosslinking agent selected from the group
consisting of
divinylbenzenes, trivinylbenzenes, divinyltoluenes, divinylxylenes,
divinylnaphthalenes divinylalkylbenzenes, divinylphenanthrenes,
divinylbiphenyls,
divinyldiphenylmethanes, divinylbenzyls, divinylphenylethers,
divinyldiphenylsulfides, divinylfurans, divinylsulfide, divinylsulfone, and
mixtures
thereof; and
iv) from 0 to about 15% by weight of a second substantially water-insoluble,
polyfunctional crosslinking agent selected from the group consisting of
polyfunctional acrylates, methacrylates, acrylamides, methacrylamides, and
mixtures thereof;
v) wherein the weight ratio of the monofunctional comonomer capable of
imparting toughness (ii) to the sum of the first and second polyfunctional
crosslinking agents (iii + iv) is at least about 1:1 preferably at least about
2:1,
more preferably at least about 3:1, and most preferably at least about 5:1;
b) from about 2 to about 15% by weight of an emulsifier component which is
soluble
in the oil phase and which is suitable for forming a stable water-in-oil
emulsion; and
2) a water phase comprising from about 0.2 to about 20% by weight of a water-
soluble electrolyte; and
3) a volume to weight ratio of water phase to oil phase of at least about
I6:1.
In another mode of the present invention the polymeric foam is produced from
an emulsion
having a water to oil weight ratio of at least about 16: l, preferably at
least about 20:1.
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In a preferred mode of the present invention the oil phase of the emulsion
comprises from
about 30 to about 65% of the monofunctional comonomer capable of imparting
toughness about
equivalent to that provided by styrene
In one convenient mode of this invention, a spot removal process is defined
using the
following steps:
1. Place the stained area of the fabric over and in fluid-receiving contact
with an abrasion
resistant stain receiver comprising polymeric foam according to his invention;
2. Apply enough composition, preferably from a bottle with a narrow spout
which directs the
composition onto the stain (without unnecessarily saturating the surrounding
area of the
fabric), to saturate the localized stained area - about 10 drops; more may be
used for a
larger stain.
3. Optionally, allow the composition to penetrate the stain for 3-5 minutes.
(This is a pre-
treat or pre-hydration step for better cleaning results.)
4. Optionally, apply additional composition - about 10 drops; more may be used
for larger
stains.
5. Apply mechanical force to the stained area. This can be done, for example,
by using the
tip of the bottle spout to mechanically manipulate the stain. Alternatively,
one can use the
spot removal device shown in the Figure to work the stain completely out. Rock
the
device (i.e. force applied in the downward "Z" direction) firmly against the
stain for 20-
120 seconds, longer for tougher stains. Do not rub {i.e., force applied in the
side-to-side
"X-Y" direction) the stain with the device, since this can harm the fabric.
6. Remove the fabric from contact with the abrasion resistant stain receiver.
7. Optionally, the fabric can be blotted with the abrasion resistant stain
receiver, with other
polymeric foams and absorbent materials, or between paper towels to remove
excess
cleaning composition.
In an alternate mode, the cleaning/refreshment composition can be applied to
the stain
(Step 2 and/or 4) by spraying, daubing or by padding the composition on from a
carrier sheet, or
by any other convenient means.
All percentages, ratios and proportions herein are by weight, unless otherwise
specified.
All documents cited are, in relevant part, incorporated herein by reference.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 illustrates the use of a cleaning device by using hand pressure to
rock the device,
thereby causing the protuberances which extend outwardly from the arcuatc,
convex head to
impinge on the stained (207) fabric and to impart a cleaning force
perpendicular to the stain. The
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polymeric foam stain receiver (501) according to this invention is shown
underlaying the stainal
' area of fabric.
DETAILED DESCRIPTION OF THE INVENTION
The stain receiver used herein comprises polymeric foams which are in the form
of water-
absorbent foams having a controlled capillary size. The physical structure and
resulting high
capillarity of polymeric foams provide very effective water absorption, while
at the same time the
chemical composition of the polymeric foam typically renders it highly
lipophilic. Thus, the
polymeric foam can essentially provide both hydrophilicity and lipophilicity
simultaneously. ('The
polymeric foams can be treated to render them hydrophilic. Both the
hydrophobic or hydrophilic
foam can be used herein.)
The acquisition and absorbency of the polymeric foam with respect to the
liquid pre-
spotting compositions herein is superior to most other types of absorbent
materials. For example,
the polymeric foam has a capacity of about 6 g (H20) per gram of foam at a
suction pressure of
100 cm of water. By contrast, cellulose wood fiber structures have essentially
no capacity above
about 80 cm of water. Since, in the present process, the volume of liquid pre-
spotter used is
relatively low (a few milliliters is typical) the amount of polymeric foam
used can 6e small. This
means that the pad of polymeric foam which underlies the stained area of
fabric can be quite thin
and still be effective.
For pre-spotting, the stained area of the garment or fabric swatch is placed
over a section
of polymeric foam, followed by treatment with the liquid cleaning solution,
preferably in
conjunction with force applied using the tip of the dispenser tube to provide
mechanical agitation.
The mechanical manipulation and the detergency effect of the solution serve to
loosen the soil and
transfer it through the fabric and into the polymeric foam. While spot
cleaning progresses, the
suction effects of the polymeric foam's capillaries cause the cleaning
solution and stain debris to
be carried into the polymeric foam, where the stain debris is largely
retained. At the end of this
step the stain, as well as almost all of the cleaning solution, is found to
have been removed from
the fabric being treated and transferred to the polymeric foam. This leaves
the fabric surface only
damp, with a minimum residue of the cleaning solution/stain debris which can
lead to undesirable
rings on the fabrics.
The polymeric foams of this invention exhibit superior abrasion resistance
when subjected
to the mechanical agitation discussed above. As used herein "abrasion
resistant" is intended to
mean the polymeric foam produces or sheds few or no small flakes that can be
transferred to the
fabric being treated. "Tearing" as used herein means the polymeric foam is
ripped or ruptured by
the mechanical force applied during the fabric treatment process. It is
important to note that
"tearing" and "abrading" are not necessarily related. Abrasion relates to the
release of small
""""-"' "'-ENCHEN 05 . 3- ~- OCA 02323875 2000-09-12136'?70260-~ X49 89 22
0303-2000 , -- ~ ---------- US 009905460
6
is intended to mean the poiyzneric foam produces or sheds few or no small
flakes that can
be transferred to the fabric being treated. "Tearing" as used herein means the
polymeric
foam is ripped or ruptured by the mechanical farce applied duriztg the fabric
ueatment
process. It is important to note that "tearing" and "abrading" arE not
necessarily related.
Abrasion relates to the release of small flakes of polymeric foam which are
both unsightly
and difficult to remove from fabrics, white tearing typically results in
substantial damage to
the polymeric foam but does not necessarily impart any undesirable effects to
the fabric
being treated. For example, a polymeric foam may have excellent abrasion
t'esistance v~~hile
being prone to 'tearing. It is generally preferred that the polymeric foams
for use in the
present invention resist bout abrasion and tearing, but the present invention
is geared
primarily to improving abrasion resistance.
llVhile the composition of the present abrasion resistant polymeric foams,
specifically, the weigl'tt percen~ge of toughening monomers attd the ratio of
toughening
monomers to cross-linking monomers, forms an integral part of the present
inventio><s, the
method of manufacturing the polymeric foam for use as the stain receiver forms
no pact of
this invention. The manufacture of polymeric foam is very extensively
described in the
patent literature; see, for example: U.S. 5,250,34> to DesMarais, Stone,
Thompson, Young,
LaVon and Dyer, issutd November 9, 1993; U.S. 5,268,224 to DesMarais, Stone,
"fhompson, Young, LaVon and Dyer, issued December 7, 1993; U.S. 5,147,345 to
Young,
LaVon and Taylor, issued September 15, 1992 and companion patent U.S. 5,3 !
8,554 issued
June 7, 1994; U.S. 5,149,720 to DesMarais, Dick and Shivcley, issued September
22, 1992
and companion patents U.S. 5,198,472, issued March 30, 1993 and lT.S.
5,250,576 issued
October 5, 1993; U.S. x,352,711 to DesMarais, issued October 4, 1994; PCT
application
93104115 published March 4, 1993, and U.S. 5,292,777 to DesMaxsis and Stone,
issued
lVtarch 8, 1994; U_5. 5,387,207 to Dyer, DesMarais, LaVon, Stone, Taylor and
Young,
issued February 7, 1995; U.S. 5,500,451 to Goldman and Scheibel, issued March
19, 1996;
$~ U.S- 5,550,157 to DesMarais, issued August 27, 1996, and U.S. 5,650,222 to
DesMarais et al., issued July 22, 1997, all incorporated herein by reference.
Typical
conditions for forming the polymeric foams of the present invention arc
described in detail
in co-pending U.S. Patent Application Serial No. 09/042,418, filed March
13,1998 by 'f. A.
DesMarais, et al. (P&G Case No. 7051 - titled "ABSORBENT M.a.'LS FOR
D1STRIBtrtiNG At?UEOUS LIQUIDS"), the ciiselosure of which is incorporated
herein by
reference.
Stain receiver pads made of polymeric foam can be used in either of two ways.
In
one mode, the uncompressed foatu is used. Uncompressed polymeric foam pads
having a
thickness in the range of abort 03 mrn to about 15 mm are useful. In another
mode, certain
polymeric foams have sufficient capillary forces such that they are 5'4able in
the compressed
AMENDED SHEET
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The preparation of polymeric foam is described in the patents cited
hereinabove. With the
exception of the discovered importance of oil phase monomer ratio that
provides improved
abrasion resistance, the processes described in the cited patents may be used
to prepare the present
foams. The following Example illustrates the preparation of a compressed foam
for use herein.
Preparation of Emulsion and Polymeric Foams Therefrom
A) Emulsion Preparation
Anhydrous calcium chloride (36.32 kg) and potassium persulfate (189 g) are
dissolved in
378 liters of water. This provides the water phase stream to be used in a
continuous process for
forming the emulsion.
The oil phase is prepared by mixing at least about 25%, preferably at least
about 30%,
and most preferably at least about 35% by weight of a toughening monomer
selected from the
group consisting of styrene, ethyl styrene and mixtures thereof with the other
optional ingredients,
such as emulsifiers, and crosslinking monomers. Preferably the weight ratio of
toughening
monomer to cross-linking monomer in the oil phase of the emulsion is greater
than about 1:1,
preferably greater than about 2:I, more preferably greater than about 3:1, and
most preferably
greater than about 5: I .
Separate streams of the oil phase (25°C) and water phase (53°-
55°C) are fed to a dynamic
mixing apparatus. Thorough mixing of the combined streams in the dynamic
mixing apparatus is
achieved by means of a pin impeller. The pin impeller comprises a cylindrical
shaft of about 36.8
cm in length with a diameter of about 2.5 cm. The shaft holds 6 rows of pins,
3 rows having 33
pins and 3 rows having 32 pins, each having a diameter of 0.5 cm extending
outwardly from the
central axis of the shaft to a length of 2.5 cm. The pin impeller is mounted
in a cylindrical sleeve
which forms the dynamic mixing apparatus, and the pins have a clearance of 1.5
mm from the
walls of the cylindrical sleeve.
A minor portion of the effluent exiting the dynamic mixing apparatus is
withdrawn and
enters a recirculation zone; see PCT U.S. 96/00082 published 18 July 96 and
EPO 96/905110.1
filed 1 I January 96. The Waukesha pump in the recirculation zone returns the
minor portion to
the entry point of the oil and water phase flow streams to the dynamic mixing
zone.
The combined mixing and recirculation apparatus set-up is filled with oil
phase and water
phase at a ratio of 4 parts water to 1 part oil. The dynamic mixing apparatus
is vented to allow
air to escape while filling the apparatus completely. The flow rates during
filling are 7.6 g/sec oil
phase and 30.3 cc/sec water phase.
Once the apparatus set-up is filled the vent is closed. Agitation is then
begun in the
dynamic mixer, with the impeller funning at 650 RPM and recirculation is begun
at a rate of about
30 cc/sec. The flow rate of the water phase is then steadily increased to a
rate of 15 I cc/sec over a
time period of about 1 min., and the oil phase flow rate is reduced to 5 g/sec
over a time period of
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about 3 min. The recirculation rate is steadily increased to about 150 cc/sec
during the latter time
period. The back pressure created by the dynamic mixer and static mixing zone
(TAH Industries
Model Number 101-212) at this point is about 4 PSI (28 kPa), which represents
the total back
pressure of the system. The Waukesha pump speed is then steadily decreased to
a yield a
recirculation rate of about 75 cc/sec.
B) Polymerization Qf Emulsion
The HIPE flowing from the static mixer at this point is collected in a round
polyethylene
tub, 40 in. ( 102 cm) in diameter and 12.5 in (31.8 cm} high, with removable
sides, much like a
springform pan used in cooking cakes. A pipe-like polyethylene insert 12.5 in
(31.8 cm) in
diameter at its base is firmly affixed to the center of the base and is 12.5
in (31.8 cm) high. The
HIPE-containing tubs are kept in a room maintained at 65° C for 18
hours to bring about
polymerization and fonm the foam.
C) Foam Washing and Dewatering
The cured polymeric foam is removed from the curing tubs. The foam at this
point has
residual water phase (containing dissolved emulsifiers, electrolyte, initiator
residues, and initiator)
about 25-35 times (25-35X) the weight of polymerized monomers. The foam is
sliced with a
sharp reciprocating saw blade into sheets which are 0.185 inches (0.47 cm) in
thickness. These
sheets are then subjected to compression in a series of 2 porous nip rolls
equipped with vacuum
which gradually reduce the residual water phase content of the foam to about 6
times (6X) the
weight of the polymerized material. At this point, the sheets are then
resaturated with a I.5%
CaCl2 solution at 60°C., are squeezed in a series of 3 porous nip rolls
equipped with vacuum to a
water phase content of about 2X. The CaCl2 content of the foam is between
about 3 and 5%.
The foam remains compressed after the final nip at a thiclrness of about 0.030
in. (0.075
cm). The foam is then dried in air for about 16 hours. Such drying reduces the
moisture content
to about 9-17 % by weight of polymerized material. At this point, the foam
sheets are very
drapeable. In this collapsed state, the density of the foam is about 0.14
g/cc. Optionally, a liquid-
impermeable backing sheet (e.g., 1 mil. polypropylene} can be applied to the
foam pad to prevent
liquid strike-through when the pad is being used.
Reinforcing Means - As noted above, for use as a stain receiver in the pre-
spotting
operation herein, a sheet of the polymeric foam is placed beneath and in close
contact with one-
side of the stained area of a fabric. A portion of pre-spotting composition is
dispensed onto the
fabric and manipulated into the stain by mechanical means. The excess pre-
spotting composition
and its load of stain material are thereby transferred into the underlying
polymeric pad. The
composition of the present polymeric foams, and specifically, the weight
percentage of toughening
monomers and the ratio of toughening monomers to cross-linking monomers,
substantially
improves abrasion resistance and minimizes flaking of the polymeric pad when
mechanical
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agitation is applied thereto. But to further minimize transfer of flakes to
the fabric being treated it
may be desirable to use reinforcing means comprising a liquid-permeable
coversheet that enrobes
the polymeric foam sheet and which freely allows passage of the liquid
cleaning composition
herein through the coversheet and into the foam.
Typical materials used as reinforcing means are as follows.
1. Formed-film material with uniform or "dual" sized holes; see, for example,
U.S.
Patents 4,324,246; 4,342,314; 4,609,518; and EP 0,165,807 for the manufacture
of formed films.
2. Poly-chiiFon - 100% polyester woven fabric.
3. 18 grams/meter2 (gsm) spunbonded polyester sheet (Reemay).
4. 18 gsm carded polypropylene sheet.
5. Women's nylon hosiery - 88% nylon, 12% Lycra~ Spandex~
6. Organza - 100% polyester woven fabric.
7. 14 gsm thermally bonded air laid woven made with bicomponent annular fiber -
polypropylene inner core with polyethylene outer shell.
*Commercially used in disposable absorbent products such as diapers.
The polymeric foam can be encased in the reinforcing means by any convenient
process
which essentially "wraps" the foam within at least one layer of the
reinforcing sheet material. If
desired, the polymeric can be only partially encased such that only the
uppenmost part of the
polymeric which is directly impacted by mechanical force during the spot-
cleaning operation is
abrasion resistant. Since the back of the polymeric may be covered with a
liquid impermeable
hacking sheet, such backing sheet will also provide reinforcement. However,
and depending on the
type of equipment which is available, it may be simpler to encase the entire
polymeric pad.
As noted, the reinforcing means can be applied to the foam pad in any
convenient manner.
Optionally, the reinforcing means can be held in place by means of adhesives,
or the like.
Preferably, the reinforcing means is applied in any manner that ensures it is
in close contact with
the polymeric pad to provide optimum reinforcement.
Compositions - The user of the present process can be provided with various
compositions
to use as spot removers. One problem associated with known fabric spot remover
compositions is
their tendency to leave visible residues on fabric surfaces. Such residues are
problematic and are
preferably to be avoided herein since the present process does not involve
conventional immersion
or rinse steps. Accordingly, the pre-spotting compositions herein should, most
preferably, be
substantially free of various polyacrylate-based emulsifiers, polymeric anti-
static agents, inorganic
builder salts and other residue-forming materials, except at low levels of
about 0.1%-0.3%, and
preferably 0%, of the final compositions. Stated otherwise the compositions
herein should be
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formulated so as to leave substantially no visible residue on fabrics being
treated according to the
practice of this invention.
Accordingly, in a preferred aspect of this invention there are provided liquid
pre-spotting
(i.e., spot-cleaning) compositions which are substantially free of materials
which leave visible
residues on the treated fabrics. This necessarily means that the preferred pre-
spotting compositions
are formulated to contain the highest level of volatile materials possible,
preferably water, typically
about 95%, preferably about 97.7%, a cleaning solvent such as BPP at a low,
hut effective, level,
typically about 1% to about 4°/g preferably about 2%, and surfactant at
levels of about 0.1 to
about 0.7%. Advantageously, when thus formulated such compositions exist as
aqueous solutions
rather than as suspensions or emulsions. Thus, such compositions do not
require use of additional
emulsifiers, thickening agents, suspending agents, and the like, all of which
can contribute to the
formation of undesirable visible residues on the fabric.
Indeed, as an overall proposition, any of the chemical compositions which are
used to
provide the pre-spotting fimction herein comprise ingredients which are safe
and effective for their
intended use, and, as noted above, preferably do not leave unacceptable
amounts of visible residues
on the fabrics. While conventional laundry detergents are typically formulated
to provide good
cleaning on cotton and cotton/polyester blend fabrics, the compositions herein
must be formulated
to also safely and effectively clean and refresh fabrics such as wool, silk,
rayon, rayon acetate, and
the like. In addition, the compositions herein comprise ingredients which are
specially selected and
formulated to minimize dye removal or migration from the stain site of
fi~gitive, unfixed dye from
the fabrics being cleaned. In this regard, it is recognized that the solvents
typically used in
immersion dry cleaning processes can remove some portion of certain types of
dyes from certain
types of fabrics. However, such removal is tolerable in immersion processes
since the dye is
removed relatively uniformly across the surface of the fabric. In contrast, it
has now been
determined that high concentrations of certain types of cleaning ingredients
at specific sites on
fabric surfaces can result in unacceptable localized dye removal. The
preferred compositions
herein are formulated to minimize or avoid this problem.
The dye removal attributes of the present compositions can be compared with
art-disclosed
cleaners using photographic or photometric measurements, or by means of a
simple, but effective,
visual grading test. Numerical score units can be assigned to assist in visual
grading and to allow
for statistical treatment of the data, if desired. Thus, in one such test, a
colored garment (typically,
sills, which tends to be more susceptible to dye loss than most woolen or
rayon fabrics) is treated
by padding-on cleaner/refresher using an absorbent, white paper hand towel.
Hand pressure is
applied, and the amount of dye which is transferred onto the white towel is
assessed visually.
Numerical units ranging from: ( 1 ) "I think I see a little dye on the towel";
(2) "I know I see some
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WO 99/46319 PCT/US99/05460
11
dye on the towel' ; (3) I see a lot of dye on the towel' ; through (4) "I
irnow I see quite a lot of dye
on the towel" are assigned by panelists.
In addition to the foregoing considerations, the compositions used herein are
preferably
formulated such that they are easily dispensed and not so adhesive in nature
that they render
dispensing from the container to be unhandy or difficult. However, and while
not intending to be
limiting of the present invention, the preferred compositions disclosed herein
afford a spot-cleaning
process which is both effective and aesthetically pleasing when used in the
manner disclosed
herein.
Aqueous Spot Stain Cleaning Compositions
(a) Water -The preferred, low residue compositions herein may comprise from
about
90%, preferably from about 95.5% to about 99.9%, by weight, of water.
(b) Solvent - The compositions herein may comprise from about 0% to about 10%,
by
weight, of butoxy propoxy propanol (BPP) solvent or other solvents as
disclosed
herein. Preferred spot cleaners will comprise 1-4% BPP.
(c) Surfactant - The compositions herein may optionally comprise from about
0.05%
to about 2%, by weight, of surfactants, such as MgAES and NH4AES, amine
oxides, ethoxylated alcohols or alkyl phenols, alkyl sulfates, and mixtures
thereof.
The use of surfactants limited to the lower end of the range is preferred for
some
dyes and fabric types. Typically, the weight ratio of BPP solventaurfactant(s)
is
in the range of from about 10:1 to about I:1. One preferred composition
comprises 2% BPP/0.25% Neodol 23 6.5. Another ureferred composition
comprises 4% BPP/0.4% AS. A highly preferred composition comprises
2% BPP/0.3% MgAEIS/0.03% dodecyldimethylamine oxide.
(d) Optionals - The compositions herein may comprise minor amounts of various
optional ingredients, including bleach stabilizers, perfumes, preservatives,
and the
like. If used, such optional ingredients will typically comprise from about
0.05%
to about 2%, by weight, of the compositions, having due regard for residues on
the
cleaned fabrics.
(e) Bleach - The compositions herein may also optionally comprise from 0% to
about
7%, by weight, of hydrogen peroxide. Preferred spot cleaners will comprise
from
0% to about 3% hydrogen peroxide. It will be appreciated that peroxide sources
other than H202 can be used herein. Thus, various per-acids, per-salts, per-
bleaches and the like known from the detergency art can be used. However, such
materials are expensive, difficult to formulate in liquid products, can leave
residues on fabrics and offer no special advantages over H202 when used in the
present manner.
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(f) Chelator - Compositions which contain H202 will also typically contain a
chelating agent. The chelating agent is selected from those which, themselves,
are
stable in aqueous H202 and which stabilize the H202 by chelating vagrant metal
ions. Such chelating agents are typically already present at low, peroxide-
stabilizing amounts (0.01-1%) in commercial sources of hydrogen peroxide. A
variety of phosphonate chelators are known in stabilizing H202. The amino
phosphonates are especially useful for this purpose. Various amino
phosphonates
are available as under the DEQUEST~ trade name from the Monsanto Company,
St. Louis, Missouri. Representative, but non-limiting, examples include
ethylenediamine tetrakis (methylene phosphoruc) acid, diethylenetriamine
penta(methylene phosphoric) acid, and the water-soluble salts thereof. Amino
tris(methylene phosphoric) acid or its water-soluble salts (as DEQUEST 2000~)
is a preferred chelator.
The pH range of the compositions helps provide stability to the hydrogen
peroxide and is
typically in the acid-slightly basic range from about 3 to about 8, preferably
about 6.
Organic Solvent - The preferred cleaning solvent herein is butoxy propoxy
propanol (BPP)
which is available in commercial quantities as a mixture of isomers in about
equal amounts. The
isomers, and mixtures thereof, are useful herein. The isomer structures are as
follows:
n-C4H9-O-CH2CH2CH2-O-CH2CH2CH2-OH
CH3
n-C4H9-O-CH2-C-O-CH2CH2CH2-OH
H
CH3
n-CQH9-O-CH2CH2CH2-O-CH2-C-OH
H
While the spot cleaning compositions herein function quite well with only the
BPP, water
and surfactant, they may also optionally contain other ingredients to further
enhance their stability.
Hydrotropes such as sodium toluene sulfonate and sodium cumene sulfonate,
short-chain alcohols
such as ethanol and isopropanol, and the like, can be present in the
compositions. If used, such
ingredients will typically comprise from about 0.05% to about 5%, by weight,
of the stabilized
compositions herein.
Surfactants - Nonionics such as the ethoxylated C 10-C 16 alcohols, e.g.,
NEODOL 23-6.5, can be used in the compositions. The alkyl sulfate surfactants
which may be
used herein as cleaners and to stabilize aqueous compositions are the Cg-C 1 g
primary ("AS' ;
preferred C 10-C 14, sodmm salts), as well as branched-chain and random C 1 p-
C20 alkyl sulfates,
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WO 99/46319 PCT/US99/05460
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and C10-Clg secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOS03 M+)
CH3 and
CH3 (CH2h,(CHOS03 M+) CH2CH3 where x and (y + 1) are integers of at least
about 7,
preferably at least about 9, and M is a water-solubilizing ration, especially
sodium, as well as
unsaturated sulfates such as oleyl sulfate. Alkyl ethoxy sulfate (AES)
surfactants used herein are
conventionally depicted as having the formula R(EO)xS03Z, wherein R is C 10-C
16 alkyl, EO is
-CH2CH2-O-, x is 1-10 and can include mixtures which are conventionally
reported as averages,
e.g., (EO)2.5, {EO)6.5 and the like, and Z is a ration such as sodium ammonium
or magnesium
(MgAES). The C 12-C 16 alkyl dimethyl amine oxide surfactants can also be
used. A preferred
mixture comprises MgAE 1 S/C 12 dimethyl amine oxide at a weight ratio of
about 10:1. Other
surfactants which improve phase stability and which optionally can be used
herein include the
polyhydroxy fatty acid amides, e.g., C 12-C 14 N-methyl glucamide. AS
stabilized compositions
preferably comprise 0.1%-0.5%, by weight, of the compositions herein. MgAES
and amine
oxides, if used, can comprise 0.01%-2%, by weight, of the compositions. The
other surfactants
can be used at similar levels.
Other Optionals - In addition to the water, the preferred BPP solvent, the
optional H202
and the surfactants disclosed above, liquid compositions used herein may
comprise various
optional ingredients, such as perfumes, preservatives, brighteners, salts for
viscosity control, pH
adjusters or buffers, and the like. The following illustrates preferred ranges
for cleaning
compositions for use herein, but is not intended to be limiting thereof.
~i ~i~t % (wt.) Formula Range
BPP (Solvent) 0.05-5
Surfactant 0-2
Perfume 0.01-1.5
Water Balance
pH range from about 6 to about 8
Other solvents or co-solvents which can optionally be used herein include
various glycol ethers,
including materials marketed under trademarks such as Carbitol, methyl
Carbitol, butyl Carbitol,
propyl Carbitol, and hexyl Cellosolve, and especially methoxy propoxy propanol
(MPP), ethoxy
propoxy propanol (EPP), propoxy propoxy propanol (PPP}, and all isomers and
mixtures,
respectively, of MPP, EPP, and BPP, as well as butoxy propanol (BP), and the
like, and mixtures
thereof. If used, such solvents or co-solvents will typically comprise from
about 0.5% to about
2.5%, by weight, of the aqueous compositions herein. Non-aqueous (less than
50% water)
compositions which optionally can be used in the pre-spotting step, can
comprise the same
solvents.
Dispenser - In one mode, the dispenser used herein comprises a container for
the liquid
pre-spotting composition, said container having a dispensing means which
comprises a spout,
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preferably in the form of a hollow tube, which is connected to said container
and is in
communication with the interior of the container. In-use, a portion of the
liquid composition within
the interior of said container flows from the container through said spout,
out the distal tip of said
spout, and onto the stain which is being treated. The user manipulates the
composition by daubing,
smearing, pressing, or the like, using the distal tip to work the composition
into the stain. A
circular, rubbing motion is typical. By this means, the composition can be
focused on the stained
area. As the stain is loosened by the combined use of the aforesaid mechanical
manipulation and
the pre-spotting composition, the stain residues and the pre-spotting
composition are transferred
away from the fabric and into the underlying stain receiver. The fabric is
then preferably re-
positioned so that a fresh area of stain receiver underlies other stained
areas, and the process is
repeated until the pre-spotting operation is completed. The fabrics can then
be used, as desired, or
otherwise laundered or dry-cleaned.
Stain Removal Device - In another mode, a preferred embodiment of the arcuate
device
shown in Figure 1, the length of the arcuate base member (403) with its
convex, generally
rectangular configuration is about 2 inches (5 cm); its width is about 1.25
inches (3.2 cm); and its
thickness is about 5/16 inch (0.8 cm). The width of shaft (404} at its mid-
point is about 1 inch
(2.54 cm) and its thickness at its midpoint is about 0.75 inch (1.9 cm). The
length of the shaft
(404) extending perpendicularly outward from the rear of the arcuate base to
the base of bulb
(405) is about 1.25 inches (3.2 cm). The bulb (405) which serves as a hand (or
palm) rest has a
circumference at its widest point of about 5.75 inches ( 14.6 cm). The
combination of shaft and
bulb thus comprise the hand grip for the device. The overall height of the
device measured from
the center of the top of the bulb (405) to the center point of the front face
of the convex base is
about 3 inches (7.6 cm). The dimensions of the sponge layer (402) and
protuberances (401) are as
given above.
Wet Abrasion Scrub Test The abrasion resistance of polymeric foams can be
measured
by the Wet Abrasion Scrub Test. A Wet Abrasion Scrub Tester can be used to
perform these
tests, and one such Tester was used for the comparative tests reported in
Example I, below.
Specifically, the Tester used to generate the data reported in Tables IA and
IB was manufactured
by Sheen, Model REF 903PG. Other methods of testing abrasion resistance and
machines for
such tests will be known to those skilled in the art.
The Sheen Wet Abrasion Scrub Tester can hold up to four bottles which are
capable of
containing fluid, and which have a blunt, convex tip for dispensing the fluid.
The bottles are
inverted so that the blunt tip is pointing downward toward, and perpendicular
(90°) to the base of
the Tester. A sheet of polymeric foam is placed on the Tester's base followed
by a fabric swatch,
which is placed on top of the polymeric sheet, and the edges of both the
polymeric sheet and the
swatch are secured so that they remain stationary during the test. A silk
swatch was used for the
CA 02323875 2000-09-12
WO 99/46319 PCT/US99/05460
IS
tests reported in Example I. A predetermined amount of fluid is then applied
to the fabric swatch.
While any amount of water or other common fluids can be selected, 3 gms of a
cleaning
composition similar to the one defined in Example II below is used for the
tests reported in
Example I. The bottle tips are then placed in contact with the fabric swatch.
The bottles can be weighted such that they apply a controlled amount of force
to the sheet
of polymeric foam. Any number of bottles and any appropriate weight can be
used. For the
comparative tests reported in Example I, thr~ bottles are used for each test,
one bottle has no load
(Ogms), the second bottle carries a 200gm load and the third bottle has a
400gm load. The Tester
then reciprocates the bottles back and forth along a straight line across the
surface of the fabric
swatch that is resting on the polymeric foam sheet. The tester can be
reciprocated for any
appropriate amount of time. At the end of the test the polymeric foam is
visually compared to a
sheet of reference polymeric foam which has undergone the same test.
The following Examples further illustrate the stain removal operation of the
present
invention, but are not intended to be limiting thereof.
EXAMPLE I
Tables IA and IB list the compositions of nine polymeric foams according to
the present
invention, and one conventional polymeric foam that was used as the reference
material.
TABLE IA
REF 1 2 3 4 5
Oil Phase
Eth 1 S ne 19 6.75 6.756.75 6.75 6.75
S n_e - 27 42.542.5 20 20
Divin lbenzene 14 8.25 8.258.25 8.25 8.25
100%
2-Eth 1-He 1 55 58 42.542.5 65 65
Ac late
Hexane Diac 12 -- -- -- - __
late
Emulsifier 7 5 6 6 6 6
A ueous Phase
cacl2 to to to to to l0
KZ O8 0.050.05 0.050.05 0.05 0.05
Ratio: A ueoualOil60 30 30 80 30 50
Tou henin monomer19 33.8 49.249.2 26.8 26.
8
Tough monomer .73 4 6 6 3.2 _
/ 3.2
Crosslink monomer
Abrasion ResistanceREF +++ +++ ++ ++ +
Tearing REF ** ** * ** _
-w"" ""~\CHE:~ 05 ~ :3- 3- O CA 02323875 2000-09-12je1TU~~u~ _-+~~_ ~s~ y 3
03-03-2000 ~-' .-- - -' ~ - US 009905460
', 16
EX
Tables IA and IB list the compositions of nine polymeric foams according to
the
present invention, and one conventional pol~tneric foam disclosed in Canadian
Patent
Application No. 2,243,731 that was used as the reference rrtaterial.
TAY~TL'T~
11 IiJL~
x~g s ~ s 9
Oil P~
Ethyl Styrene 19 G.75 6.75 6.756.75
Styrene -- 27 2? ?7 27
Divinylbenzene 14 8 8.25 8.258.25
{100%) 55 ~5 58 53 53
2-Eth 1-Hex71 12 58 -
Acrylate 7 - 6 6 6
Hexane Diacrylate 6
Emulsifier
Aqueous Phase
CaC 30 10 10 10 10
0.050.05 0.05 0_05O.OS
Ratio: ( ueoustOit)60 30 44 30 60
Toughoning monomer19 33.8 33.8 33.833.8
Tough monomer .73 4 4 2.5 2.5
I
Crosslink monomtr
Abrasion Resistance
?eariag REF s - ** "*
The Abrasion Resistance and Tearing tests are conducted versus the Reference
polymeric
foam. The ratings are based on visual comparis4ns of polymeric foam subjected
to the Wet
AMENDED SHEET
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17
(a) underlaying the area containing said stain with the absorbent, polymeric
foam stain
receiver reinforced with non-woven spun-bonded polyester fabric, basis weight
ca.
18 grams/meter2;
(b) applying a liquid cleaner (pre-spotter) composition to said stain from a
container having a
dispenser spout; and
(c) rubbing or pressing said cleaning composition into said stain using the
distal tip of said
spout, whereby said stain is transferred into the abrasion resistant polymeric
stain
receiver.
In this mode, the face of the distal tip of said spout can be concave, convex,
flat, or the
like. The combination of container plus spout is referred to herein conjointly
as the "dispenser".
A typical dispenser herein has the following dimensions, which are not to be
considered
limiting thereof. The volume of the bottle used on the dispenser is typically
2 oz. - 4 oz. (fluid
ounces; 59 mls to 118 mls). The larger size container bottle can be high
density polyethylene.
Low density polyethylene is preferably used for the smaller bottle since it is
easier to squeeze. The
overall length of the spout is about 0.747 inches (1.89 cm). The spout is of a
generally conical
shape, with a diameter at its proximal base (where it joins with the container
bottle) of about 0.596
inches ( 1.51 cm) and at its distal of 0.182 inches (4.6 mm). The diameter of
the channel within the
spout through which the pre-spotting fluid flows is approximately 0.062 inches
( 1.57 mm). In this
embodiment, the channel runs from the container bottle for a distance of about
0.474 inches
(1.2 cm) and then expands slightly as it communicates with the concavity to
form the exit orifice at
the distal end of the spout.
Compositions for use herein with the aforesaid dispenser and the abrasion
resistant
polymerized foam stain receiver is as follows.
INGREDIENT Nonionic Comn. Anionic Comn.
(%) (%)
Hydrogen peroxide I I
Amino tris(methylene phosphoruc acid)* 0.04 0.05
Butoxypropoxypropanol (BPP) 2 2
Neodol 23 6.5 0.3 ____
NH4 Coconut E 1 S --- 0.3
Dodecyldimethylamine oxide --- 0.03
Magnesium chloride ---- 0.02
Magnesium sulfate ---- 0.02
Hydrotrope, perfume, other minors, ---- 0.1
Kathon preservative 0.0003 0.0003
Water (deionized or distilled) 96.6 96.5
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WO 99/46319 PCT/US99/05460
18
Target pH** 6.0 6.0
*Stabilizer for hydrogen peroxide
**Range pH 5-8
EXAMPLE III
Examples of preferred, high water content, low residue compositions for use
herein are as
follows. The compositions are listed as "nonionic" or "anionic", depending on
the type of
surfactant used therein.
lngredien Nonionic (%) Anionic (%)
Butoxypropoxypropanol (BPP) 2.00 2.00
NEODOL 23 6.5 0.250 ---
NH4Coconut E1S* --- 0.285
Dodecyldimethylamine oxide --- 0.031
MgCl2 --- 0.018
MgS04 --- 0.019
Hydrotrope, perfume,
other minors --- 0.101
KATHON preservative 0.0003 0.0003
Water 97.750 97.547
*Ammonium salt of C12-C14 (coconut allryl) ethoxy (EO-1) sulfate.
In a highly preferred mode, the liquid Nonionic or Anionic composition is
applied to the
stained area from a dispenser in the manner of Example I to remove stain from
fabrics.
