JP2002506100A - Abrasion-resistant polymeric foam material and dye receiver produced therefrom - Google Patents

Abstract

(57) Abstract: Abrasion resistant dye receivers made of polymeric foam materials (polymeric foam materials are made from oil and water emulsions, wherein the oil phase of the emulsion is at least about 30% by weight of styrene, ethyl styrene and Or a toughening monomer selected from the group consisting of mixtures thereof). Preferably, the abrasion resistant dying comprises a crosslinkable monomer selected from the group consisting of divinylbenzene, hexanediacrylate and mixtures thereof, wherein in the oil phase of the emulsion, the toughening and crosslinking monomers are combined. The weight ratio is greater than about 1: 1. The polymeric foam material is resistant to peeling when used as a dye receiver in a textile dye removal operation.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to a foam-resin receiver with improved abrasion resistance used for spot cleaning of fabrics.

BACKGROUND fabric cleaning and recovery process of the invention, for example, laundry and dry cleaning operations are commonly used in cleaning the entire garment. However, the user may want to clean only a localized area of the fabric. Alternatively, a user may wish to comprehensively dry clean or wash the entire garment after cleaning the localized areas of the fabric.

[0003] Certain absorbent polymeric foam materials are particularly effective in spot cleaning operations.
I know. These polymeric foams have high internal phase emulsions (High I nternalPhaseEmulsions) (hereinafter referred to as HIPE). For example, US Pat.
, 260, 345 (DesMarais et al.), Promulgated November 9, 1993, U.S.A.
National Patent No. 5,268,224 (DesMarais et al.), December 7, 1993
DYER '207 describes a polymeric foam material generally promulgated from HIPE
And DESMARAIS'222 (both included here for reference). Typical operation
In the polymeric foam material, a liquid cleaning composition is passed through the stained / dyed area of the fabric.
It functions as a “dyeing tray” by sucking things. For example, depending on the cleaning composition
The separated dirt / dye is captured in the polymeric foam material. the important thing is,
It minimizes the tendency of the polymeric foam material to spread laterally on soiled / dyed fabrics.
This minimizes the "ring" formation on the fabric.

[0004] In a preferred spot washing operation, a polymeric foam material receiver is positioned below the dye area of the fabric. The cleaning composition is then applied to the dye and penetrated into the dye by mechanical action. Such mechanical action preferably comprises using a compressing, mainly Z-directional force in the manner disclosed herein. Here, it has been determined that the previously disclosed polymeric foam material, when used as a dye receiver, may not be strong enough to withstand the strong forces applied during the cleaning operation. . Briefly, the polymeric dye receiver is so fragile under mechanical force that it begins to collapse, which may cause the polymeric foam material to flake off. For this reason, the appearance of the area where the spot cleaning process is performed becomes messy. Moreover, undesired flakes of polymeric foam material may migrate to the fabric being spot washed.

[0005] One method of solving the problems associated with prior art foam material dyeing is described in US Patent Application Serial No. 60 / 053,191. This application relates to a polymeric foam material dye receiver wrapped in a cover sheet. This method of protecting a polymeric foam material is effective, but increases the cost and processing steps of the dye receiving production. Thus, there remains a need for an improved polymeric foam material dyke that can withstand abrasion and does not exfoliate or collapse during use.

[0006] Having discovered the problems associated with polymeric foam materials when used in the current manner, the present invention uses a new composition for polymeric dyeing, thereby minimizing such problems. It is to suppress.

[0007] BACKGROUND International Patent No. WO97 / 00993A1, published Jan. 9, 1997, We
ller et al., International Patent Publication No. WO 97 / 00990A2, published Jan. 9, 1997, Tycrech et al., British Patent No. 2,302,553A, 199.
Published January 22, 1995, Telesca, et al., UK Patent No. 2,302,878A, published February 5, 1997, Weller et al., And UK Patent No. 2,302.
No., 879A, published Feb. 5, 1997, Sidoti et al. (All related to fabric washing in dryers). U.S. Pat. No. 5,432,722, Aug. 1985
Promulgated on June 6, SH Sax, relates to fabric conditioning equipment used in laundry dryers. Peracid-containing dry cleaning compositions are disclosed in US Pat. No. 4,013,575,
Published March 22, 977, issued to H. Castrantas, et al. The dry cleaning method is described in US Pat. No. 5,547,476, Aug. 20/9.
6, issued to Siklosi and Roetker, US Pat. No. 5,591,236,
Published by Roetker on 1/7/97, U.S. Pat. No. 5,630,847.
Published by Roetker on 20/97, U.S. Pat. No. 5,630,848, 5/2
U.S. Pat. No. 5,632,780, issued to Young, et al.
/ 27/97, published in Siklosi, European Patent Application No. 429,172A1, 2,. 05.91, Leigh, et al. And US Pat. No. 5,238,5.
No. 87, promulgated 8/24/93, Smith, et al. Other documents relating to dry cleaning compositions and methods, and wrinkling of fabrics include:
UK Patent 1,598,911 and US Patent 4,126,563
No. 3,949,137, No. 3,593,544, No. 3,647,354, No. 3,432,253 and No. 1,74.
7,324, and German Patent Application Nos. 2,021,561 and 2,460,239, 0,208,989 and 4,0.
No. 07,362. The cleaning / prestainer composition and method comprises:
For example, U.S. Patent Nos. 5,102,573, 5,041,230, 4,909,962, 4,115,061, and 4,88.
No. 6,615, No. 4,139,475, No. 4,849,257, No. 5,112,358, No. 4,659,496, No. 4,
, 806,254, 5,213,624, 4,130,3
No. 92, and No. 4,395,261. Sheet substrates for use in laundry dryers are disclosed in Canadian Patent No. 1,005,204. U.S. Pat. Nos. 3,956,556 and 4,007,3.
No. 00 relates to a perforated sheet for fabric conditioning in a fabric dryer. U.S. Pat. No. 4,692,277 discloses the use of 1,2-octanediol in a liquid cleaner. U.S. Pat.No. 3,591,510,
U.S. Pat. Nos. 3,737,387, 3,764,544;
No. 3,882,038, 3,907,496, 4,097,3.
No. 97, No. 4,102,824, No. 4,336,024, No. 4,594,362, No. 4,606,842, No. 4,75
Nos. 8,641, 4,797,310, 4,802,997, 4,943,392, 4,966,724, and 4
No. 5,983,317, 5,004,557, 5,062,9.
No. 73, No. 5,080,822, No. 5,173,200, European Patent No. 0213500, and European Patent No. 026171.
8, British Patent 1,397,475, International Patent WO 91/0
No. 9104, WO 91/13145, WO 93/25654
And Hunt, DG and NH Morris, "PnB and DPnB glycol ethers", HAPPI , April 1989, pp. 78-82.

SUMMARY OF THE INVENTION The present invention encompasses a polymeric foam material and an abrasion resistant dye receiver comprising the polymeric foam material, wherein the polymeric foam material comprises: 1) an oil phase [the oil The phases include: a) from about 85 to about 98% by weight of a monomer component, the monomer component comprising: i) from about 25 to about 70% by weight of a substantially water-insoluble,
Ii) from about 25% to about 65% by weight of a monofunctional comonomer capable of imparting toughness substantially insoluble in water and substantially equivalent to that provided by styrene. Iii) about 5 to about 25% by weight of divinylbenzene, trivinylbenzene,
Selected from the group consisting of divinyltoluene, divinylxylene, divinylnaphthalene, divinylalkylbenzene, divinylphenanthrene, divinylbiphenyl, divinyldiphenylmethane, divinylbenzyl, divinylphenylether, divinyldiphenylsulfide, divinylfuran, divinylsulfide, divinylsulfone, and mixtures thereof. And iv) from 0 to about 15% by weight of a polyfunctional acrylate, methacrylate, acrylamide, methacrylamide, and mixtures thereof. V) a monofunctional comonomer (ii) capable of imparting toughness and a first and second polyfunctional crosslinker comprising a second substantially water-insoluble polyfunctional crosslinker selected from: The weight ratio of the sum (iii + iv) is at least about : 1, preferably at least about 2: 1, more preferably at least about 3: 1, and most preferably at least about 5:
1) and b) from about 2 to about 15% by weight of an emulsifier that is soluble in the oil phase and is suitable for forming a stable water-in-oil emulsion], and 2) about 0. An aqueous phase comprising from 2 to about 20% by weight of a water-soluble electrolyte; and 3) a polymerized water-in-oil emulsion having a volume ratio of aqueous phase to oil phase of at least about 16: 1. .

In another mode of the invention, the polymeric foam material is made from an emulsion having a weight ratio of water to oil of at least about 16: 1, preferably at least 20: 1.

In a preferred embodiment of the invention, the oil phase of the emulsion comprises from about 30 to about 65% of a monofunctional comonomer capable of imparting toughness approximately equivalent to that provided by styrene.

In a convenient mode of the present invention, the dyeing process is performed by the following steps. 1. The dyed area of the fabric is placed in contact with the liquid to receive the liquid on the abrasion resistant dye receiver comprising the polymeric foam material of the present invention. 2. Sufficient composition is applied (preferably without saturating the peripheral area of the fabric unnecessarily) from a bottle having a narrow spout that directs the composition onto the dye, and saturates the locally dyed area (About 10 drops, more can be used for larger dyes). 3. If desired, the composition is allowed to soak in the dye for 3-5 minutes. (This is a pre-treatment or pre-hydration step to get better cleaning results.) If desired, apply additional composition (about 10 drops, more can be used for larger dyes). 5. Apply mechanical force to the dyed area. This can be done, for example, by mechanically rubbing the dye using the outlet of the bottle. Alternatively, the dye can be completely treated using the dye removing device shown in the figure. The device is pressed firmly against the dye and rocks back and forth (i.e., applies force in the downward "Z" direction), typically for 20-120 seconds, longer for persistent dye. Do not rub the fabric with the device (i.e., do not apply a lateral "XY" force) as it may damage the fabric. 6. Pull the fabric away from contact with the abrasion resistant dye receiver. 7. Optionally, with an abrasion resistant dye, with another polymeric foam and absorbent material,
Alternatively, wipe the fabric between paper towels to remove excess cleaning composition.

In another manner, the cleaning / healing composition is applied to the dye by spraying, smearing, or padding the composition from a carrier sheet, or by other conventional means (step 2 and / or 4) Yes.

Unless otherwise indicated, all percentages, ratios and proportions given herein are by weight. All cited documents are relevant and are hereby incorporated by reference.

[0014] receiving dyeing used herein Detailed description of the invention comprises a polymeric foam material in the form of a water-absorbing foam material which adjust the size of the capillary. The physical structure of the polymeric foam and the resulting high capillarity give it very effective water absorption, while at the same time the chemical composition of the polymeric foam gives it a high degree of lipophilicity I do. Thus, the polymeric foam material simultaneously provides substantially both hydrophilicity and lipophilicity. (The polymeric foam material can be treated to render it hydrophilic. Both hydrophobic and hydrophilic foam materials can be used.) Liquid pre-dyeing of the polymeric foam material The acquisition and absorbency for the punch composition is superior to most other types of absorbent materials. For example, the present polymeric foam material has a capacity of about 6 g (H ₂ O) per gram of foam material at a suction pressure of 100 cm of water. In contrast, cellulosic wood fiber structures have substantially no volume above about 80 cm of water. In the process of the present invention, the volume of the polymeric foam material used may be small since the volume of the pre-dyeing agent used is relatively low (typically a few milliliters). That is, the pad of polymeric foam material underneath the dyed area of the fabric may be very thin and still be effective.

For pre-dyeing, the dyed area of the garment or piece of cloth is placed on a portion of the polymeric foam material and then forced with a liquid cleaning solution, preferably using the tip of a metering device tube. And processing with mechanical stirring. This mechanical manipulation and cleaning effect of the solution lifts the soil and migrates through the fabric into the polymeric foam material. As the spot cleaning progresses, the washing solution and the debris of the dye are carried into the polymeric foam by the suction effect of the capillary of the polymeric foam, and the debris of the dye are largely transferred into the polymeric foam. Partially retained. After this step, almost all of the dyeing, as well as the cleaning solution, is removed from the treated fabric and sent to a polymeric foam. This leaves only the wetness on the fabric surface and leaves little cleaning solution / dying debris that can form unwanted rings on the fabric.

[0016] The polymeric foam material of the present invention exhibits excellent wear resistance when subjected to the mechanical stirring described above. As used herein, "abrasion resistance" means that little or no small flakes can migrate to the fabric being treated. As used herein, "tearing" means that the polymeric foam material is cut or broken by the mechanical forces applied during the fabric treatment process. It is important to note that "tearing" and "wearing" are not necessarily related. Abrasion is associated with the release of small flakes of polymeric foam material, which impart an unsightly appearance and are difficult to remove from the fabric, while tearing typically involves a polymer. It causes severe damage to the cellular foam material, but does not necessarily have an undesirable effect on the fabric being treated. For example, polymeric foam materials, while having excellent wear resistance, may be prone to tearing. In general, it is preferred that the polymeric foam used in the present invention be resistant to both abrasion and tearing, but the present invention is tailored primarily to improve abrasion resistance.

The composition of the abrasion-resistant polymeric foam material of the present invention, in particular, the weight percentage of the toughness imparting monomer and the ratio of the toughness imparting monomer to the cross-linking monomer constitute an essential part of the present invention, The process for producing the polymeric foam material used as dye receiver does not constitute any part of the present invention. The production of polymeric foam materials has been very extensively disclosed in the patent literature, for example, see US Pat. No. 5,2,2, all of which are incorporated herein by reference.
No. 60,345, Nov. 9, 1993, DesMarais, Stone, Thompson,
U.S. Pat. No. 5,268,224, issued to Young, LaVon and Dyer, 19
U.S. Pat. No. 5,147,345 issued to DesMarais, Stone, Thompson, Young, LaVon and Dyer on Dec. 7, 1993, Young, L. on Sep. 15, 1992.
issued to aVon and Taylor, and related patents US Pat. No. 5,318,554, issued on Jun. 7, 1994, US Pat. No. 5,149,720, 199
U.S. Pat. No. 5,198,472 issued to DesMarais, Dick, and Shiveley on Sep. 22, 2002, and related patents issued on Mar. 30, 1993 and U.S. Pat. No. 5,250,576. , Promulgated on October 5, 1993, U.S. Pat.
No. 352,711, issued to DesMarais on Oct. 4, 1994, PCT Application No. 93/04115, published Mar. 4, 1993, and US Pat.
U.S. Pat. No. 5,387,207, issued to DesMarais, and Stone on Mar. 8, 1994, U.S. Pat. No. 5,387,207, issued to Dyer, DesM on Feb. 7, 1995.
arais, LaVon, Stone, Taylor and Young, US Patent No. 5,500,4
No. 51, issued to Goldman and Scheibel on March 19, 1996; U.S. Pat. No. 5,550,167; issued to DesMarais on August 27, 1996;
And U.S. Patent No. 5,650,222, issued July 22, 1997 to DesMar.
Promulgated and referenced in ais et al. Typical conditions for forming the polymeric foam material of the present invention are described in pending U.S. patent application Ser. No. 7, submitted by TA DesMarais, et al. On March 13, 1998 (P & G Case No. 7
051-titled "Absorptive materials for distributing aqueous liquids").

Dye receiving pads made of polymeric foam material can be used in one of two ways. One mode uses an uncompressed foam material. An uncompressed polymeric foam pad having a thickness of about 0.3 mm to about 15 mm is effective. In another mode, certain polymeric foam materials have sufficient capillary forces,
Stable in compressed state. Such foam materials are described above in '207 and' 2.
No. 22 patent. These foam materials can be used in a compressed state and swell as the liquid pre-dye containing dyeing substance is sucked. Alternatively, the Tg of the foamed material may be much higher than the use temperature and remain compressed (compositions 2 and 3 in Table IA). Here, the thickness is about 0.5 mm to about 4.7.
mm compressed polymeric foam material is preferred.

The production of the polymeric foam material is described in the patents cited above. Apart from the discovered importance of the oil phase monomer ratio to improve abrasion resistance, the process described in the above patents can be used to produce the foamed material. The following example illustrates the manufacture of the compressed foam material used herein.

Preparation of the Emulsion and the Polymeric Foam Therefrom A) Preparation of the Emulsion Anhydrous calcium chloride (36.32 kg) and potassium persulfate (189 g) are dissolved in 378 liters of water. This gives an aqueous phase flow for the continuous production of the emulsion.

The oily phase comprises at least about 25%, preferably at least about 30%, and most preferably at least about 35% by weight of a toughening monomer selected from styrene, ethylstyrene and mixtures thereof. By mixing with optional components such as emulsifiers and crosslinking agents. Preferably, the weight ratio of the toughening and crosslinking monomers in the oil phase of the emulsion is about 1: 1.
More than 1, preferably more than about 2: 1, more preferably more than about 3: 1 and most preferably more than about 5: 1.

Separate streams of the oil phase (25 ° C.) and the aqueous phase (53-55 ° C.) are fed to a dynamic mixer. The streams mixed in the dynamic mixer can be mixed well using a pin impeller. The pin impeller comprises a cylindrical shaft about 36.8 cm long and about 2.5 cm in diameter. The shaft holds 6 rows of pins, 3 rows has 33 pins, 3 rows has 32 pins, each pin is 0.5cm in diameter and is outward from the central axis of the shaft To a length of 2.5 cm. The pin impeller is
Mounted in a cylindrical sleeve forming a dynamic mixing device, the pin has a gap of 1.5 mm from the wall of the cylindrical sleeve.

[0023] A small amount of effluent is removed from the dynamic mixing device and placed in a recirculation zone (PCT US 96/00082, published July 18, 1996 and 1996).
(See EPO 96 / 905110.1, filed January 11, 2011). A Waukesha pump in the recirculation zone returns this small portion to the entry point of the oil and water phases into the dynamic mixing zone.

The combined mixing and recirculation unit is filled with an oil phase and an aqueous phase in a ratio of 4 parts water to 1 part oil. While the dynamic mixing device is completely filled, vent the device to allow air to escape. The flow rate during the filling is 7.6 g / sec for the oil phase and 30.3 cc / sec for the aqueous phase.

When the assembled device is full, close the vent. Stirring is then started at 650 RPM of the impeller and recirculation is started at a rate of about 30 cc / sec in the dynamic mixer. The flow rate of the aqueous phase is then uniformly increased to a rate of 151 cc / sec over about 1 minute, and the flow rate of the oil phase is reduced to 5 g / sec over about 3 minutes. During this time, the recirculation speed
Increases uniformly to 50 cc / sec. Dynamic mixer and static mixing area (TAH Industri
The back pressure created at this point by the es Model Number 101-212) is about 4 PSI (28 kPa), which represents the total back pressure of the system. The Waukesha pump speed is then reduced uniformly to a recirculation rate of about 75 cc / sec.

B) Emulsion polymerization At this point, the HIPE flowing out of the static mixer was 40 inches (102 cm) in diameter.
), Collected in a 12.5 inch (31.8 cm) high, round polyethylene container with removable sides, much like a spring foam pan used for cooking cakes. A 12.5 inch (31.8 cm) diameter pipe-shaped polyethylene insert at the bottom is firmly fixed in the center of the bottom and has a height of 12.5 inches (31.8 cm).
cm). The container containing the HIPE is kept in a room maintained at 65 ° C. for 18 hours and polymerized to form a foamed material.

C) Cleaning and Dehydration of the Foamed Material The polymer foamed material is removed from the curing container. The foam material at this point is
It has a residual aqueous phase (including dissolved emulsifier, electrolyte, initiator residue, and initiator) of about 25-35 times (25-35X) the weight of polymerized monomer. The foam material is sliced into 0.185 inch (0.47 cm) thick sheets with a reciprocating sharp saw blade. The sheets are then compressed with a series of two-porous nip rolls equipped with a vacuum device to gradually reduce the residual aqueous phase content of the foamed material to about six times (6X) the polymerized material. At this point, the sheet is resaturated with a 1.5% CaCl ₂ solution at 60 ° C. and squeezed with a series of three porous nip rolls equipped with a vacuum device to a water phase content of about 2 ×. The CaCl ₂ content of the foamed material is about 3-5%.

The foam material remains compressed about 0.030 inch (0.075 cm) thick after the final nip. The foam material is then dried in air for about 16 hours. Such drying reduces the water content to about 9-17% by weight of the polymerized material. At this point, the foam sheet is very pliable. In this collapsed state, the density of the foam material is about 0.14 g / cc. If desired, a liquid impermeable backing sheet (eg, 1 mil polypropylene) can be applied to the foam pad to prevent liquid penetration when the pad is used.

Reinforcing means As mentioned above, for use as a dye receiver in a pre-dyeing operation, a sheet of polymeric foam material is placed in intimate contact under one side of the dye receiving area of the fabric. A small amount of the pre-dyed composition is dispensed onto the fabric and rubbed into the dye by mechanical means. This transfers the excess pre-dye composition and the dyestuffs contained therein into the underlying polymeric foam material. The composition of the present polymeric foam material, especially the weight percentage of the toughness imparting monomer and the toughness imparting monomer to crosslinkable monomer weight ratio, when mechanical action is applied to the pad, the polymer pad Greatly improves wear resistance and minimizes delamination. However, to further suppress the transfer of flakes to the fabric being treated, a liquid permeable coversheet wrapping the polymeric foam material sheet is included, and the liquid composition of the present invention is passed through the coversheet to form the foamed material. It is preferable to use a reinforcing means that allows free passage through the inside.

Typical materials used as reinforcing means are shown below. 1. Molded film material with uniform or "double" size holes. Regarding the formed film, for example, US Pat. Nos. 4,324,246 and 4,342,
No. 314, No. 4,609,518 and European Patent No. 0,059.
See 165,807. 2. Poly-chiffon-100% polyester non-woven fabric. 3.18 g / m ^{2 (gsm)} spunbond processed polyester sheet over preparative (Reemay). 4.18 gsm carded polypropylene sheet. ^* 5. Women's nylon socks-88% nylon, 12% Lycra (brand name) Spandex (
Product name). 6. Organza-100% polyester woven fabric. 7.14 gsm thermal bonded air-laid woven fabric of bicomponent annular fibers (polypropylene inner core and polyethylene outer shell). ^* Commercially used for disposable absorbent products, such as diapers.

The polymeric foam material can be contained within the reinforcing means in any convenient manner that substantially “wraps” the foam material within at least one layer of the reinforcing sheet material. If desired, the polymer foam is only partially accommodated so that only the uppermost portion of the polymer foam to which mechanical force directly acts during the spot cleaning operation is abrasion resistant. You can also. The back side of the polymeric foam material can be coated with a liquid impermeable backing sheet, so that such a backing sheet is also reinforced. However, depending on the type of equipment available, it may be easier to house the entire polymeric pad.

As mentioned above, the reinforcement means can be applied to the foam pad in any convenient manner. If desired, the reinforcing means can be held in place by an adhesive or the like. Preferably, the reinforcing means is mounted in any manner that ensures intimate contact with the polymeric pad and provides an optimum reinforcing effect.

Compositions The user of the present method can use various compositions as dye removers. One of the problems associated with known fabric dyeing compositions is that they tend to leave visible residues on the fabric surface. Since no conventional dipping or rinsing step is performed in the present invention, such residues are difficult to dispose of and are preferably avoided here. Accordingly, the pre-dyed composition of the present invention is most preferably substantially free of various polyacrylate-based emulsifiers, polymeric antistatic agents, inorganic builder salts, and other residue-forming materials. Even at low levels of about 0.1% to 0.3% of the final composition, preferably 0%. In other words, the compositions of the present invention should be formulated so as to leave substantially no visible residue on the material being processed in accordance with the practice of the present invention.

Accordingly, a preferred embodiment of the present invention provides a liquid pre-dye (ie, spot wash) composition that is substantially free of materials that leave a visible residue on the treated fabric. This necessarily entails that preferred pre-dye compositions have as high a level as possible, typically about 95%, preferably about 97.7%, of volatile material, preferably water,
Low, but effective, typically about 1% to about 4%, preferably about 2%,
Of a cleaning solvent, such as BPP, and about 0.1 to about 0.7% of a surfactant. Advantageously, when so formulated, such compositions are present as aqueous solutions, not suspensions or emulsions. for that reason,
Such compositions do not require additional emulsifiers, thickeners, suspending agents, etc., all of which lead to the formation of undesirable, visible residues on the fabric.

Indeed, in general terms, any of the chemical compositions used herein to provide a pre-dye function comprise components that are safe and effective for their intended use, and as described above. Preferably, no unacceptable amounts of visible residue remain on the fabric. Whereas conventional laundry detergents are typically formulated to provide good cleaning on cotton and cotton / polyester blend fabrics, the compositions of the present invention provide wool, silk, rayon, Fabrics such as rayon acetate must also be formulated to be safe and effective. In addition, the compositions of the present invention are specifically selected to minimize the migration of dye or the migration of unfixed floating dye from dyed spots on the fabric being washed; Comprising the prescribed ingredients. In this regard, it has been found that solvents typically used in immersion dry cleaning processes can remove some of the dyes from certain fabrics. However, in the dipping process, such removal is acceptable because the dye is removed relatively uniformly throughout the fabric. In contrast, it has been found that unacceptable local dye removal can occur when certain cleaning components are present at high concentrations at specific locations on the fabric surface. Preferred compositions of the present invention are formulated to minimize or avoid this problem.

The dye removability of the present compositions can be compared to prior art detergents using photographic or photometric measurements or by a simple but effective visual grading test. If desired, numerical scoring units can be specified, visual grading can be facilitated, and statistical processing of the data can be performed. For example, in one such test, colored garments (typically silk, which tends to be more sensitive to dye loss than most wool or rayon fabrics) are used with absorbent white paper hand towels. Use and treat with padding-on-cleaner / refresher. Apply pressure by hand,
Visually assess the amount of dye that has migrated onto the white towel. Judges (1) "I think there is a small amount of dye on the towel", (2) "I see a certain amount of dye on the towel", and (3) "I see a large amount of dye on the towel" , (4) Specify a numerical unit up to “Too many dyes are visible on the towel”.

In addition to the above considerations, the compositions used herein are preferably easily metered,
Formulate so as not to be so viscous that it is difficult to dispense it from the container. However, while not intending to limit the invention, the preferred compositions disclosed herein provide an effective and aesthetically pleasing spot cleaning method when used in the manner disclosed herein.

Aqueous Dye Spot Cleaning Composition (a) Water-A preferred low residue composition of the present invention comprises from about 90% by weight, preferably from about 95.5 to about 99.9% by weight of water. Can be. (B) Solvents-The composition can comprise from about 0 to about 10% by weight of a butoxypropoxypropanol (BPP) solvent or other solvent disclosed herein. Preferred spot cleaners comprise 1-4% BPP. (C) Surfactant - The compositions, optionally, from about 0.05 to about 2 wt% surfactant, eg MgAES and _NH 4 AES, amine oxides, ethoxylated alcohols or alkyl phenols, alkyl sulfates, and their A mixture of For certain dyes and fabrics it is preferred to use a surfactant at the lower end of this range. Typically, the weight ratio of BPP solvent: surfactant is from about 10: 1 to about 1: 1. A preferred composition is 2% BPP / 0.2
5% Neodol 236.5. Another preferred composition is 4% BPP / 0.4
5% AS. A very preferred composition is 2% BPP / 0.3% MgA
E ₁ comprising S / 0.03% dodecyl dimethyl amine oxide. (D) Optional Ingredients-The composition can comprise small amounts of various optional ingredients, including bleach stabilizers, fragrances, preservatives, and the like. When used, such optional ingredients typically comprise from about 0.05 to about 2% by weight of the composition, taking into account residues on the washed fabric. (E) Bleach-The composition can also optionally comprise from 0 to about 7% by weight of hydrogen peroxide. Preferred spot cleaners comprise 0 to about 3% hydrogen peroxide. Of course, peroxide sources other than H ₂ O ₂ can also be used here. For example, various peracids, persalts, overbleaches and the like known in the detergent field can be used. However, such materials are expensive, difficult to formulate in liquid products, can leave residues on textiles, and have an advantage over H ₂ O ₂ when used in the manner of the present invention. There is no particular sex. (F) a composition comprising a chelating agent -H ₂ O ₂ typically also includes a chelating agent. Chelating agents themselves aqueous H are stable at ₂ O ₂ in, by chelating metal ions to float, is selected from the agents to stabilize the H ₂ O _2.
Such chelating agents are typically already present in commercial hydrogen peroxide sources in low, peroxide stabilizing amounts (0.01-1%). For stabilizing H ₂ O ₂ , various phosphonate chelating agents are known. Aminophosphonates are particularly effective for this purpose. Various aminophosphonates are available at Monsanto Compa
It is commercially available from ny, St. Louis, Missouri under the name DEQUEST (trade name). Representative examples include, but are not limited to, ethylenediaminetetrakis (methylenephosphonic) acid, diethylenetriaminepenta (methylenephosphonic) acid, and water-soluble salts thereof. Aminotris (methylenephosphonic) acid or a water-soluble salt thereof (eg, DEQUEST 2000 (trade name)) is a preferred chelating agent.

The pH range of the composition helps to provide stability to the hydrogen peroxide and is typically about 3 to about 8 acidic to slightly basic, preferably about 6.

Organic Solvent The preferred washing solvent here is butoxypropoxypropanol (BPP), which is commercially available as a mixture of approximately equal amounts of isomers. Isomers and mixtures thereof are useful herein. The isomer structures are as follows.

Embedded image

The spot cleaning composition of the present invention works very well with BPP, water and surfactant alone, but may optionally include other components to further enhance their stability. Hydrotropic agents such as sodium toluenesulfonate and sodium cumenesulfonate, short chain alcohols such as ethanol and isopropanol, and the like can be present in the composition. When used, such components typically comprise from about 0.05 to about 5% by weight of the stabilized composition.

[0042] Surfactant nonionic substances, such as ethoxylated _C 10 _{-C 16} alcohols, for example NEOD
OL 23-6.5 can be used in the composition. Use as a detergent, an alkyl sulfate surfactant capable of stabilizing an aqueous composition C ₈ -C ₁₈ primary ( "
AS ", preferably _C 10 _{-C 14} sodium salt), and branched-chain and random _C 10 _{-C 20} alkyl sulfates, and the formula _{CH 3 (CH 2) x (} CHOS O 3 - M +) CH 3 and CH ₃ ( ^{_{CH 2) y (CHOSO 3 -}} M +) CH 2 CH 3 ( wherein, x and (y + 1) is at least about 7, preferably at least about 9 integer, M is a cation, in particular to impart water solubility C ₁₀ )
_C18 secondary (2,3) alkyl sulfates, as well as unsaturated sulfates such as oleyl sulfate. As used herein, alkyl ethoxy sulfate (AES) surfactant is represented as a substance having the formula R (EO) _x SO ₃ Z,
Wherein R is C ₁₀ -C ₁₆ alkyl, EO is —CH ₂ CH ₂ —O—, x is 1 to 10, and the mixture is usually reported as an average, such as (EO) _{2. 5,} it is possible to include _{(EO) 6.5,} etc., Z is a cation such as sodium, ammonium or magnesium (MgAES). C ₁₂ -C ₁₆ alkyl dimethyl amine oxide surfactants can also be used. A preferred mixture is M
gAE ₁ S / C ₁₂ dimethylamine oxide in a weight ratio of about 10: 1.
Improved phase stability, other surfactants can be optionally used herein include polyhydroxy fatty acid amides, for example C _{12 -C} 14 _N-methyl glucamide, a.
The AS stabilizing composition preferably comprises from 0.1 to 0.5% by weight of the composition.
MgAES and amine oxides, when used, make up from 0.01 to 2% by weight of the composition. Other surfactants can be used at similar levels.

Other Optional Components In addition to water, a preferred BPP solvent, optional H ₂ O ₂ and the above-described surfactants, the liquid compositions used herein may comprise various optional components. For example, a fragrance, a preservative, a brightener, a viscosity adjusting salt, a pH adjusting agent or a buffer, and the like can be included. Preferred ranges for the cleaning composition used herein are shown below, but are not limited thereto. Component formulation range (% by weight) BPP (solvent) 0.05-5 Surfactant 0-2 Fragrance 0.01-1.5 Water Remaining pH range about 6-about 8

[0044] Other solvents or co-solvents which may optionally be used here include various glycol ethers, such as Carbitol, methyl Carbitol, butyl Carbitol, propyl Carbitol.
And materials marketed under the trade names such as hexyl Cellosolve, and especially methoxypropoxypropanol (MPP), ethoxypropoxypropanol (
EPP), propoxypropoxypropanol (PPP), and MPP, EP
And the respective isomers and mixtures of P and BPP, and butoxypropanol (BP), and the like, and mixtures thereof. When used, such solvents or co-solvents typically comprise from about 0.5 to about 2.5% by weight of the aqueous composition. Non-aqueous (less than 50% water) compositions that can optionally be used in the pre-dyeing step can comprise the same solvent.

[0045] In the dispenser one mode, dispenser used herein comprises a container for a liquid pre-stain removal compositions, the container has a metering means comprising a discharge port, said The outlet is preferably in the form of a hollow tube, connected to the container and in communication with the inside of the container. In use, a portion of the liquid composition inside the container flows from the container through the outlet and out of the outlet onto the dye being treated. The user operates the tip by applying, rubbing, pressing, or the like using the tip to infiltrate into the dye. A circular friction motion is typical. By this means, the composition can be concentrated in the dyeing area. As the dye is lifted by the combined use of the above mechanical operations and the pre-dye composition, the dye residue and the pre-dye composition migrate from the fabric into the underlying dye receiver. The fabric is then preferably repositioned so that a new area of dyeing is below another area of dyeing, and the process is repeated until the pre-dyeing operation is complete. The fabric can then be used or washed or dry cleaned, if desired.

Dye Removal Apparatus In another preferred embodiment of the arcuate apparatus shown in FIG. 1, the length of the convex, generally rectangular arcuate base member (403) is about 2 inches (5 cm). And its width is about 1.25 inches (3.2 cm) and its thickness is about 5/16 inches (0.3 cm).
8 cm). The width of the shaft (404) at the midpoint is about 1 inch (2.5
4 cm), and the thickness at the midpoint is about 0.75 inches (1.9 cm). The length of the shaft (404) extending perpendicularly outward from the rear of the arcuate base toward the base of the bulb (405) is about 1.25 inches (3.2 cm). The circumference of the bulb (405) on which the hand (or palm) rests is about 5.75 inches (14.6 cm) at its widest point. Thus, the combination of the shaft and the bulb constitutes the handgrip of the device. The total height measured from the center of the top of the bulb (405) to the center of the front of the convex foundation is about 3 inches (7.6 cm). Sponge layer (402)
The dimensions of the ridge (401) are as described above.

Wet Abrasion Test The abrasion resistance of the polymeric foam material can be measured by a wet abrasion test. These tests can be performed using a wet abrasion tester, and such a tester was used in the comparative tests described in Example I below. Specifically, the tester used to obtain the data reported in Tables IA and IB was a Model REF 90 manufactured by Sheen.
3PG. Other methods of testing wear resistance and machines for performing such tests are known to those skilled in the art.

Sheen's Wet Abrasion Tester can hold liquid and can hold up to four blunt, convex-tip bottles for dispensing liquid. The bins are inverted so that the blunt tip points downward and is at a right angle (90 °) to the base of the tester. Place the sheet of polymeric foam material on the base of the tester, and then place a piece of cloth on the polymeric sheet, securing both the polymeric sheet and the piece of cloth immovably during the test. I do. A piece of silk cloth was used for the test reported in Example I. Apply a predetermined amount of liquid to a piece of cloth. Although any amount of water or other common liquid can be selected, 3 grams of a cleaning composition similar to the composition defined in Example II below is used for the test reported in Example I. The tip of the bottle is then brought into contact with the piece of cloth.

The bottle can be loaded such that a controlled amount of force is applied to the sheet of polymeric foam material. Any number of bins and any suitable load can be used. In the comparative test shown in Example I, three bins were used for each test, one bin was not loaded (0 gm), the second bin was loaded with 200 gm, and the third bin was loaded. Puts a load of 400 gm. The test apparatus then reciprocates the bottle back and forth across the surface of the piece of cloth over the sheet of polymeric foam material. The tester can be reciprocated at any suitable time. At the end of the test, the polymeric foam material is visually compared with a sheet of a reference polymeric foam material that has undergone the same test.

[0050]

【Example】

The following examples further illustrate, but do not limit, the dyeing operation of the present invention.

EXAMPLE I Tables IA and IB show the composition of nine polymeric foam materials according to the present invention and one conventional polymeric foam material used as a reference material.

[0052]

[Table 1]

[Table 2]

Abrasion resistance and tear tests are performed on a reference polymeric foam material. Evaluation,
This is done by visual comparison of the polymeric foam material subjected to the above wet abrasion test. Each polymeric foam material, including the reference, is tested at 0 gm, 200 gm and 400 gm. The results of the three tests for each polymeric foam were compared to the three for the reference polymeric foam.
Compare with the test of the time. Guidelines for abrasion resistance evaluation +++ = Excellent abrasion resistance ++ = Excellent abrasion resistance + = Slightly excellent abrasion resistance Guidelines for tear evaluation ** = Little or no tearing * = Slight There was severe tearing but less tearing than standard-= More tearing than standard

EXAMPLE II A spot washing operation to remove dye from a localized area of the fabric was performed by: (a) Spunbonded nonwoven polyester fabric (about 18 grams basis weight) beneath the area containing the dye / B) arranging an absorptive polymeric foam material reinforced with / m ² ), (b) applying a liquid detergent (pre-dyeing agent) composition to the dye from a container having a metering outlet, And (c) rubbing or pushing the cleaning composition into the dye using the tip of the discharge port to transfer the dye into the abrasion resistant polymeric dye receiver.

In this manner, the surface at the tip of the outlet may be concave, convex or flat, etc. The combination of the container and the outlet is collectively referred to herein as a "metering device".

Here, a typical dosing device has, but is not limited to, the following dimensions: The volume of the bottle used in the dosing device is typically 2 oz. To 4 oz. (Oz. Liquid, 59 ml. To 118 ml.). Larger containers may be made of high density polyethylene. Low density polyethylene is preferably used for small bottles because it is easy to squeeze. The total length of the outlet is about 0.747 inches (1.89 cm). The outlet is generally conical and the base (where it connects to the container bottle) has a diameter of about 0.596.
Inches (1.51 cm) and the tip is 0.182 inches (4.6 mm). The diameter of the passage in the outlet through which the pre-dye fluid flows is about 0.062 inches (1.
57 mm). In this embodiment, the passage extends about 0.474 inches (1.2 cm) from the bottom of the container and then slightly widens where it communicates with the depression, forming an outlet orifice at the end of the outlet.

The compositions used in the metering device and the dye-resistant polymeric foam material receiver are as follows. Component non-ionic anionic composition composition (%) (%) Hydrogen peroxide 1 1 Amino tris (methylene phosphonic ^{acid) *} 0.040 0.05 butoxypropoxypropanol (BPP) 2 2 Neodol 23 6.5 0.3 ---- NH 4 Coconut E ₁ S ---- 0.3 Dodecyldimethylamine oxide ---- 0.03 Magnesium chloride ---- 0.02 Magnesium sulfate ---- 0.02 Hydrotropes, fragrances and other minor ingredients ---- 0.1 Kathon preservative 0.0003 0.0003 Water (deionized or distilled) 96.6 96.5 Target pH ^** 6.0 6.0 ^* Stabilizer for hydrogen peroxide ^** pH range 5-8

Example III A preferred high water content, low residue composition for use herein is shown below. This composition is described as "nonionic" or "anionic", depending on the type of surfactant used therein. Component non-ionic anionic butoxy propoxy propanol (BPP) 2.00 2.00 NEODOL 23 6.5 0.250 --- NH 4 Coconut _E 1 ^{S *} --- 0.285 dodecyl dimethyl amine oxide _{--- 0.031 MgCl 2 --- 0.018 MgSO 4} - - 0.019 hydrotropes, perfumes, other minor ingredients --- 0.101 KATHON preservative 0.0003 0.0003 water 97.750 97.547 ^* C ₁₂ ~C ₁₄ (coconut alkyl) ethoxy (EO-1) ammonium salts of sulfates

In a very preferred manner, the liquid nonionic or anionic composition is applied to the dyeing area from a dosing device in the manner of Example I to remove the dye from the fabric.

[Brief description of the drawings]

FIG. 1 illustrates the use of hand pressure to oscillate a cleaning device back and forth, applying a protrusion extending outwardly from an arc-shaped convex head to a fabric with a dye (207), This shows how the detergency is applied at right angles. Polymeric foam material dye receiver of the present invention (501)
Is below the dyed area of the fabric.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission Date] March 3, 2000 (200.3.3)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

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[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

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The composition of the abrasion-resistant polymeric foam material of the present invention, in particular, the weight percentage of the toughness-imparting monomer and the ratio of the toughness-imparting monomer to the crosslinking monomer constitute an essential part of the present invention, The process for producing the polymeric foam material used as dye receiver does not constitute any part of the present invention. The production of polymeric foam materials has been very extensively disclosed in the patent literature, for example, see US Pat. No. 5,2,2, all of which are incorporated herein by reference.
No. 60,345, Nov. 9, 1993, DesMarais, Stone, Thompson,
U.S. Pat. No. 5,268,224, issued to Young, LaVon and Dyer, 19
U.S. Pat. No. 5,147,345 issued to DesMarais, Stone, Thompson, Young, LaVon and Dyer on Dec. 7, 1993, Young, L. on Sep. 15, 1992.
issued to aVon and Taylor, and related patents US Pat. No. 5,318,554, issued on Jun. 7, 1994, US Pat. No. 5,149,720, 199
U.S. Pat. No. 5,198,472 issued to DesMarais, Dick, and Shiveley on Sep. 22, 1993, and related patents issued on Mar. 30, 1993 and U.S. Pat. No. 5,250,576. , Promulgated on October 5, 1993, U.S. Pat.
No. 352,711, issued to DesMarais on Oct. 4, 1994, PCT Application No. 93/04115, published Mar. 4, 1993, and US Pat.
U.S. Pat. No. 5,387,207, issued to DesMarais, and Stone on Mar. 8, 1994, U.S. Pat. No. 5,387,207, issued to Dyer, DesM on Feb. 7, 1995.
arais, LaVon, Stone, Taylor and Young, US Patent No. 5,500,4
No. 51, issued to Goldman and Scheibel on March 19, 1996; U.S. Pat. No. 5,550,167; issued to DesMarais on August 27, 1996;
And U.S. Pat. No. 5,650,222, issued Jul. 22, 1997 to DesMar.
Promulgated and referenced in ais et al. Typical conditions for forming the polymeric foam material of the present invention are described in pending U.S. patent application Ser. No. 09/04, the disclosure of which is incorporated herein by reference.
2,418, filed March 13, 1998 by TA DesMarais, et al. (P &
G Case No. 7051-Title "Absorptive materials for distributing aqueous liquids").

[Procedure amendment 3]

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Example I Tables IA and IB show nine polymeric foams according to the invention and one conventional polymeric foam used as a reference material (Canadian Patent Application No. 2,243).
, 731).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06F 43/00 D06F 43/00 A (71) Applicant ONE PROCTER & GANBL E PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Thomas, Allen, Desmaleis, United States Ohio, Cincinnati, Skull, Road, 10204 (72) Inventor Bruce, Albert, Jesel, Ohio, United States of America, Cincinnati, Winstead, Lane, 10115 F-term (reference) 3B116 AA46 AB51 BA01 BB21 BC05 CC03 3B155 AA02 CC20 GA01 GA05 GA25 4H003 AB31 AC08 AC15 BA20 BA23 DA03 DB01 DC04 EA12 EA19 EB24 ED02 ED29 EE04 FA28 4J011 JB30 LA04 LA06 LA08 LA09 LB01 LB09 4J100 AB02Q AB04Q AB15R AB16R AL04P AL62S AP02R AQ01R BA02R BA51R BA58R CA05 CA06 FA20 JA00 JA57

Claims (9)

[Claims] 1. A polymeric foam comprising a polymerized water-in-oil emulsion, comprising: 1) an oil phase, comprising: a) 85-98% by weight of a monomer component; The components are i) 25 to 70% by weight of a substantially water-insoluble, monofunctional monomer capable of forming a polymer having a Tg of 25 ° C. or less; ii) 25 to 65% by weight of a substantially A monofunctional comonomer which is insoluble in water and which can impart toughness almost equivalent to that provided by styrene, and iii) 5 to 25% by weight of divinylbenzene, trivinylbenzene, divinyltoluene, divinylxylene, divinylnaphthalene. , Divinylalkylbenzene, divinylphenanthrene, divinylbiphenyl, divinyldiphenylmethane, divinylbenzyl, divinylphenylether, divinyldiphenylsulfur A first substantially water-insoluble multifunctional crosslinking agent selected from the group consisting of: divinylfuran, divinylsulfide, divinylsulfone, and mixtures thereof; and iv) A second substantially water-insoluble polyfunctional crosslinker selected from the group consisting of functional acrylates, methacrylates, acrylamides, methacrylamides, and mixtures thereof; and v) a monofunctional comonomer capable of imparting toughness characterized in that the weight ratio of (ii) to the sum of the first and second polyfunctional crosslinking agents (iii + iv) is at least 1: 1 and b) from 2 to 15% by weight Water characterized by an emulsifier that is soluble in the oil phase and is suitable for forming a stable water-in-oil emulsion; and 2) water characterized by 0.2 to 20% by weight of a water-soluble electrolyte. With the phase, and 3) A polymeric foam material having a volume such that the weight ratio of aqueous phase to oil phase is at least 16: 1. 2. The composition of claim 1, wherein the weight ratio of the monofunctional comonomer (ii) capable of imparting toughness and the sum of the first and second polyfunctional crosslinkers (iii + iv) is at least 2: 1. A polymeric foam material as described. 3. The composition of claim 1, wherein the weight ratio of the monofunctional comonomer (ii) capable of imparting toughness to the sum of the first and second polyfunctional crosslinkers (iii + iv) is at least 3: 1. A polymeric foam material as described. 4. The composition according to claim 1, wherein the weight ratio of the toughness-imparting monofunctional comonomer (ii) to the sum of the first and second polyfunctional crosslinking agents (iii + iv) is at least 5: 1. A polymeric foam material as described. 5. The polymeric foam of claim 1, wherein the oil phase of the emulsion comprises from 30 to 65% by weight of a monofunctional comonomer capable of imparting toughness equivalent to that provided by styrene. material. 6. An abrasion-resistant dye receiver comprising the polymeric foam material according to claim 1. 7. An abrasion-resistant dye receiver comprising the polymeric foam material according to claim 2. 8. An abrasion resistant dye receiver characterized by a polymeric foam material comprising a polymerized water-in-oil emulsion, comprising: 1) an oil phase; and a) 85-98. % By weight of a monomer component, the monomer component comprising: i) 25 to 70% by weight of a monofunctional monomer capable of forming a substantially water-insoluble polymer having a Tg of 25 ° C. or less; ii) 25 to 65% by weight of a substantially water-insoluble monofunctional comonomer capable of imparting toughness similar to that provided by styrene; iii) 5 to 25% by weight of divinylbenzene, trivinyl Benzene, divinyltoluene, divinylxylene, divinylnaphthalene, divinylalkylbenzene, divinylphenanthrene, divinylbiphenyl, divinyldiphenylmethane, divinylbenzyl, divinylphenylether, A first substantially water-insoluble polyfunctional crosslinking agent selected from the group consisting of vinyl diphenyl sulfide, divinyl furan, divinyl sulfide, divinyl sulfone, and mixtures thereof; and iv) 0 to 15% by weight A second, substantially water-insoluble, multifunctional crosslinker selected from the group consisting of multifunctional acrylates, methacrylates, acrylamides, methacrylamides, and mixtures thereof; v) providing toughness Characterized in that the weight ratio of the monofunctional comonomer (ii) to the sum of the first and second multifunctional crosslinkers (iii + iv) is at least 1: 1; and b) 15% by weight of an emulsifier that is soluble in the oil phase and is suitable for forming a stable water-in-oil emulsion; and 2) 0.2-20% by weight of a water-soluble electrolyte. Special And the aqueous phase, and 3) the aqueous phase and the weight ratio of the oil phase is at least 16: and a volume to be 1, receiving the wear resistance dyeing. 9. A method for cleaning a dyed area, comprising: (a) contacting the dyed area of the fabric with the dye-resistant area on the abrasion-resistant dye receiver according to claim 7 or 8; (B) applying sufficient cleaning composition to saturate the locally stained area; (c) allowing the composition to penetrate the dye for 3-5 minutes, if desired; (D) applying an additional composition, if desired; (e) exerting a mechanical force on the dyed area; (f) pulling the fabric out of contact with the dye receiver; and (g) 2.) A method, if desired, by wiping the fabric between paper towels or with other absorbent material to remove excess cleaning composition.