Laundry devices for delivering dye transfer inhibiting benefits

Information

  • Patent Grant
  • 6521582
  • Patent Number
    6,521,582
  • Date Filed
    Wednesday, June 12, 2002
    22 years ago
  • Date Issued
    Tuesday, February 18, 2003
    21 years ago
Abstract
A laundry device for use with a washing machine is provided. The laundry device includes a bag storing a water-insoluble DTI compound. The bag includes a plurality of apertures allowing wash water to flow through the bag but which substantially prevent the water-insoluble DTI compound from exiting the bag during use. The laundry device can further include a container having a compartment for receiving and dispensing a dosed amount of detergent during use.
Description




TECHNICAL FIELD OF THE INVENTION




The present invention relates to the field of devices for use with a laundering process, and, more particularly, to the field of laundry devices for storing dye transfer inhibiting compounds.




BACKGROUND OF THE INVENTION




The laundering of colored garments is a delicate operation. Dye bleeding from fabrics and dye transfer between fabrics during the laundering process can lead to the undesirable result of color alteration of the laundered garments. The use of dye transfer inhibiting (DTI) compounds is known in the art as a means for reducing the effects of dye transfer between laundered articles. These DTI compounds, which can be provided in the form of polymers, have the ability to complex or absorb the fugitive dyes washed out of fabrics before the dyes have the opportunity to attach to other articles in the wash. Some DTI compounds include vinylpyrrolidone polymers, polyamine N-oxide polymers and copolymers of vinylpyrrolidone and N-vinylimidazole. These polymers can be water soluble or substantially water insoluble, as described in U.S. Pat. No. 5,912,221 issued to Van Leeuwen et al. on Jun. 15, 1999, the substance of which is fully incorporated herein by reference, and can be added directly to the wash water if desired. However, when too much of a DTI compound is present in the wash water, it can negate the effectiveness of laundry brighteners or fluorescent whitening agents as well as negatively impact the cleaning performance of a laundry detergent. Excessive amounts of a DTI compound in the wash water may also cause deterioration of non-extraneous dyes present on the items being laundered. In other words, even dyes that do not ordinarily give rise to bleeding in the wash water can be attacked by a DTI compound, resulting in faded or non-uniform appearances of the laundered items.




It is also known in the art to chemically bond dye scavenging compounds to a substrate, such as by covalently bonding a polyquaternary ammonium compound to a cellulosic material as described in U.S. Pat. No. 5,881,412 to Ziskind. U.S. Pat. No. 4,380,453 to Claiborne also describes an article impregnated with a dye scavenging compound. In practice, however, it has been determined that the above-described dye-scavenging approach requires an impractical size for the substrate to reduce bleeding to manageable or even acceptable levels, and is restrictive in terms of possible substrate candidates that are compatible with the dye scavenging compounds.




Yet another approach taken to reduce dye transfer during a wash process is discussed in U.S. Pat. No. 4,494,264 to Wattiez et al., wherein articles subject to dye bleeding are physically separated from the remaining laundry articles by an envelope. This approach, however, can suffer from the inconvenience of having to sort items into a confining laundry envelope, resulting in decreased cleaning due to restricted movement of the enveloped items through the wash water. In addition, this approach does not appear to provide a mechanism for restricting dye transfer among the articles within the envelope.




Therefore, there is a desire to provide methods and devices for delivering dye transfer inhibiting benefits with a simplified laundry device. Further, there is a desire to provide a laundry device which eliminates contact between the laundered articles and the DTI compound. Yet further, there is a desire to provide a laundry device which can deliver DTI benefits as well as dispense a laundry detergent. Still yet further, there is a desire to provide a laundry device which can deliver DTI benefits, wherein the DTI compound can be replaced so that the laundry device is useable over multiple washing cycles.




SUMMARY OF THE INVENTION




A laundry device for use with a washing machine is provided. The laundry device includes a bag storing a water-insoluble DTI compound. The bag includes a plurality of apertures allowing wash water to flow through the bag but which substantially prevent the water-insoluble DTI compound from exiting the bag during use. The laundry device can further include a container having a compartment for receiving and dispensing a dosed amount of detergent during use.











BRIEF DESCRIPTION OF THE DRAWINGS




While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description taken in conjunction with the accompanying drawings in which:





FIG. 1

is an exploded perspective view of a preferred laundry device made in accordance with the present invention;





FIG. 2

is a cross-sectional side view of the assembled laundry device of

FIG. 1

, taken along line


2





2


thereof;





FIG. 3

is a perspective view of a preferred bag suitable for storing a water-insoluble DTI compound;





FIG. 4

is partial cross-sectional side view of the laundry device of

FIG. 2

, wherein a liquid detergent is shown dispensed into the device;





FIG. 5

is an exploded perspective view of another preferred laundry device made in accordance with the present invention;





FIG. 6

is a cross-sectional side view of the laundry device of

FIG. 5

, taken along line


6





6


thereof;





FIG. 7

is a perspective view of the laundry device of

FIG. 5

, wherein the bag is illustrated in its swollen state;





FIG. 8

is an exploded perspective view of yet another preferred laundry device made in accordance with the present invention;





FIG. 9

is a cross-sectional side view of the assembled laundry device of

FIG. 8

, taken along line


9





9


thereof, and





FIG. 10

is perspective view of a bag made in accordance with the present invention, wherein a portion of the bag has been removed to expose a compartment storing a water-insoluble DTI compound.











DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS




Unless specifically indicated otherwise, those figures expressed in terms of percent (%) are understood to refer to weight-percent. Reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings wherein like numerals indicate the same elements throughout the views and wherein reference numerals having the same last two digits (e.g.,


20


and


120


) connote similar elements. As discussed more fully hereafter, the present invention is directed to water permeable laundry devices having a water-insoluble dye transfer inhibiting (DTI) compound stored therein, and, more preferably, to laundry devices for dispensing laundry products, such as liquid, tablet, or powder detergents, and which further include a replaceable bag having a water-insoluble DTI compound stored therein. The laundry devices of the present invention can be used with any type of automatic washing machine, including washing machines with and without an agitator. Further, the laundry devices can freely float within the wash volume of the washing machine or can be fixedly attached to the interior of the washing machine tub.




In accordance with one aspect of the present invention and with reference to

FIGS. 1

,


2


, and


3


, a preferred laundry device


20


is illustrated. The laundry device


20


has a frame


22


, a connector


24


, a bag


26


with compartment


27


storing a water-insoluble DTI compound


29


, and a retainer


28


. The frame


22


is substantially annular in shape and includes an opening


30


and a plurality of feet


32


which provide a stable platform for the laundry device


20


when it is placed upon a surface. The frame


22


has a radially extending ledge


34


located adjacent to the opening


30


. An inner wall


35


depends downwardly from the ledge


34


and has a female thread


36


disposed thereabout. The connector


24


is provided in the form of a ring having, in addition to the male thread


37


disposed about the outer surface of the connector


24


, a female thread


38


disposed about the inner surface of the connector


24


for engaging a male thread


40


of the retainer


28


. The retainer


28


includes a radially outwardly extending flange


41


which engages the ledge


34


when the laundry device


20


is assembled. The connector


24


has a radially inward extending lip


42


with one or more concentric ridges


44


disposed about the upper surface of the lip


42


. When the laundry device


20


is assembled, an extension


48


(

FIG. 3

) of the bag


26


is disposed between the ridges


44


and a one or more ridges


46


disposed on a radially inwardly extending lip


47


of the retainer


28


. The combination of and cooperation between the ridges


44


and the ridges


46


secure the bag


26


to the dosing device


20


during use.




The upper wall


50


of the bag


26


is preferably provided in the form of a depression and, more preferably, is substantially hemispherical in shape for receiving a liquid or powder detergent


52


(

FIG. 4

) therein. As such, the upper wall


50


is preferably formed from a material which is impermeable to the liquid detergent


52


, such as polypropylene, polyethylene, or polyamide films. As best seen in

FIG. 3

, the lower wall


54


of the bag


26


includes a plurality of apertures


56


through which the laundry wash water can flow but which restrict movement of the water-insoluble DTI particles


29


from the compartment


27


of the bag


26


into the washing volume of a washing machine. While the apertures


56


are illustrated as discrete portions of the lower wall


54


for clarity, it will be understood that more or less than the entire lower wall


54


may contain the apertures


56


. As used herein, the term “apertures” is intended to refer to any random or predetermined opening through which the wash water can flow. For example, the apertures


56


can be randomly formed as part of a non-woven fabric or can be formed as part of predetermined discrete pattern. The apertures


56


are sized to prevent the water-insoluble DTI compound


29


from exiting the compartment


27


of the laundry device


20


and preferably have an average aperture open area (i.e., the area through which the wash water can flow) which is less than about 20 mm


2


and, more preferably, is between about 4×10


−3


mm


2


and about 5 mm


2


. The total open area of the apertures


56


of the lower wall


54


is at least about 20 mm


2


and, more preferably, is between about 50 mm


2


and about 500×10


3


mm


2


. For apertures formed as non-discrete patterns (e.g., such as in a non-woven fabric), the aperture open area can be characterized according to the air permeability of the material forming the wall, as measured by ISO method 9237. The air permeability of the material forming the wall


54


is at least about 100 L/m


2


/s and more preferably is at least about 500 Lm


2


/s. Most preferably, the air permeability of the material forming the wall


54


is at least about 1000 L/m


2


/s. The volume of the compartment


27


is at least about 1 cm


3


and, more preferably, between about 5 cm


3


and about 1000 cm


3


which is sufficient to store between about 1 g and about 500 g of the water-insoluble DTI compound


29


. This amount of DTI compound can be sufficient for between about 1 and about 20 uses in a standard wash cycle lasting 10 to 120 minutes. More preferably, the water-insoluble DTI compounds confined in the compartment of the bag of the laundry devices of the present invention, when tested according the Dye Removal Test Method described more fully hereafter, remove at least about 10% of the test dye after 15 wash test cycles and more preferably at least about 25% of the test dye at 15 wash test cycles. Most preferably, the DTI compounds confined in the compartment of the bag of the laundry devices of the present invention remove at least about 50% of the test dye after 15 wash test cycles. The volume of the compartment


27


can be increased or decreased to accommodate more or less of the water-insoluble DTI compound


29


as desired. The compartment


27


can be permanently sealed such that the bag


26


is discarded when the DTI compound


29


has become ineffective or the bag


26


can be fitted with a resealable closure, as known in the art, so that the ineffective DTI compound


29


can be emptied from the compartment


27


of the bag


26


and the compartment


27


refilled with new DTI compound


29


. For example, a zipper or a hook and loop type closure could be fitted to the bag


26


.




The laundry devices of the present invention can be used with a variety of liquid, granular or tablet laundry detergents where it is desirable to deliver dye-transfer benefits. Exemplary liquid laundry detergents include those disclosed in U.S. Pat. No. 5,275,753, issued Jan. 4, 1994, to Boutique et al., U.S. Pat. No. 5,223,179, to Connor et al., issued Jun. 29, 1993 and U.S. Pat. No. 5,565,145, to Watson et al., issued Oct. 15, 1996, all of which are incorporated by reference. Also useful are the nonaqueous liquid laundry detergents exemplified by U.S. Pat. No. 5,945,392, issued Aug. 31, 1999, to Boutique et al., hereby incorporated by reference.




In addition to liquid detergent products, water-insoluble detergent products may also be used with the laundry devices of the present invention. Examples of suitable water-insoluble detergent products are the granular detergent products disclosed in U.S. Pat. No. 5,762,647, to Brown et al., issued Jun. 9, 1998 and the compact detergent products of U.S. Pat. No. 5,691,294, to France et al., issued Nov. 25, 1997, both of which are incorporated by reference. Also suitable as water-insoluble detergents are granular products compressed into a tablet form such as those described in U.S. Pat. No. 4,219,435, to Biard et al., issued Aug. 26, 1980 and European Patent Application No. 896,053A1, published Feb. 2, 1999, both of which are incorporated by reference. Another type of laundry product which may be used with the laundry devices of the present invention is liquid fabric softener products, such as U.S. Pat. No. 5,804,219, to Trinh et al., issued Sep. 8, 1998, which is hereby incorporated by reference.




The laundry device


20


is assembled by first positioning the bag


26


so that the extension


48


of the bag


26


is disposed over the lip


42


of the connector


24


. The retainer


28


is then threadedly advanced into the connector


24


until the lip


47


of the retainer


28


engages the extension


48


of the bag


26


such that the grooves


46


and ridges


44


cooperate to secure the bag


26


to the combination of the connector


24


and the retainer


28


. This combination is then threadedly advanced into the opening


34


of the frame


22


until the flange


41


of the retainer


28


engages the ledge


34


of the frame


22


. As shown in

FIG. 4

, the liquid laundry detergent


52


is poured through the opening


30


of the frame


22


and into the depression formed by the inner wall


50


of the bag


26


. A compartment


59


storing the liquid laundry detergent


52


is formed by a combination of the upper wall


50


of the bag


26


and the inner surface


58


of the retainer


28


, as best seen in FIG.


4


. The upper wall


50


of the bag


26


as well as the inner surface


58


of the retainer


28


can be provided with dosing lines to assist in dispensing predetermined amounts of the laundry detergent


52


into the laundry device


20


. As will be appreciated, the ridges


44


and grooves


46


, in addition to securing the bag


26


to the laundry device


20


, also provide a substantially liquid tight seal at the bag, connector, and retainer interface so that the liquid laundry detergent


52


does not leak out of the compartment


59


. The frame


22


, connector


24


, and retainer


28


can be formed from a thermoplastic material, such as polyethylene, polystyrene, or nylon, by injection molding.




Referring to

FIGS. 5 and 6

, another preferred laundry device


120


made in accordance with the present invention is illustrated. The laundry device


120


comprises a bag


126


generally in the form of ring and a container


60


having a compartment


159


for storing, for example, the liquid detergent


52


. The container


60


has an opening


134


through which the liquid detergent


52


is poured into compartment


159


. The circumference of the container


60


increases in the direction from the opening


134


of the container


60


toward the mid-section of the container. The container


60


also includes a groove


62


at about the midpoint of the container which cooperates with an elastomeric retaining ring


64


disposed adjacent the opening


67


of the bag


126


. The retaining ring


64


is used to secure the bag


126


about the laundry device


120


during use. The inside circumference of the retaining ring


64


, when the ring


64


is in a relaxed state, is preferably less than the smallest circumference of the groove


62


. The laundry device


120


is assembled by sliding the bag


126


over the upper portion of the container


60


until the retaining ring


64


cooperates with the groove


62


of the container


60


. As the bag


126


traverses the upper portion of the container


60


, the opening


67


of the bag


126


expands to accommodate the increasing circumference of the container


60


. Because the inside circumference of the retaining ring


64


when the ring


64


is in a relaxed state is preferably less than the smallest circumference of the groove


62


, the retaining ring


64


will be in tension when it engages the groove


62


. This force retains the bag


126


about the laundry device


120


during use in a washing machine. Some DTI compounds of this invention exhibit the property to swell when exposed to water or to a wash medium. A schematic representation of such swelling is illustrated in FIG.


7


. The swelling can, in some cases, reach 200 to 300% of the volume of the DTI compound in its dry state. For example, polyvinyl N-oxide (PVNO) cross linked by about 0.5% (w/w) of divinylbenzene (DVB) over a DTI monomer can swell up to about 200% of its original volume. Typically, the degree of swelling is related to the degree of cross linking, wherein the greater the degree of cross linking, the lower the amount of swelling which occurs. As such, the dimensions or the material of the bag can be chosen in such a way that the bag can accommodate the swelling of the DTI compound without rupturing. For instance, the inner and/or outer walls


150


and


154


of the bag


126


can be made from an elastic material which can accommodate the swelling. Alternately, the volume of the compartment


127


of the bag


126


can be sized to accommodate the swelling of the DTI compound.




The container


60


can be formed by injection molding from polyethylene or any other material as is known in the art. The inner and outer walls


150


and


154


of bag


126


are preferably formed from non-woven, spun-bonded or spun-bonded/melt-blown sandwich polypropylene while the elastomeric ring


64


can be formed from any elastomer which is compatible with the liquid detergent


52


, as is known in the art. The inner and/or outer walls


150


and


154


of the bag


126


have a plurality of apertures


56


which allow adequate flow of the wash water into the compartment


127


of the bag


126


which stores the water-insoluble DTI compound


29


in order to deliver the dye transfer inhibiting benefit. As previously discussed with respect to the laundry device


20


, however, the apertures


56


retain the water-insoluble DTI compound


29


within the compartment


127


of the bag


126


during use.




Referring to

FIGS. 8 and 9

, yet another preferred laundry device


220


made in accordance with the present invention is illustrated. The laundry device


220


includes a container


160


with a compartment


259


for storing the liquid detergent


52


. A chamber


66


is disposed adjacent to the compartment


259


for receiving a bag


226


having a water-insoluble DTI compound (not illustrated). The chamber


66


is preferably closed by a lid


68


attached by a hinge


72


to the container


160


adjacent the opening


130


of the container


160


. The lid


68


further includes a securing mechanism, such as a clip, prong, or other structure known in the art, for releasably securing the lid


68


in a closed position to retain the bag


226


within the chamber


66


during use in a washing machine. The lid


68


and/or one or more of the outside walls (i.e., walls which are exposed to the wash water) which form the chamber


66


contain a plurality of slits


70


which allow the wash water to flow into and out of the chamber


66


so that the bag


226


can deliver a DTI benefit to the wash water.




While the laundry devices of the present invention are described herein as comprising a bag in combination with a container which can also dose a laundry detergent to the wash water during use, the bags of the present invention can also be used individually by merely placing the bag directly in the wash water of the washing machine, or by attaching it to the drum or the agitator of the washing machine through mechanical or other means. For example, as shown in

FIG. 10

, a bag


326


having a plurality of apertures


56


and storing a water-insoluble DTI compound


29


could be placed directly in the wash water. Preferably, the water-insoluble DTI compound


29


of the bag


326


would comprise a solid cross-linked polyvinyl N-oxide, as discussed more fully hereafter. Bags made in accordance with the present invention which are suitable for use individually can be provided in a variety forms, but will at least contain a compartment for storing a water-insoluble DTI compound and have a plurality of apertures, as previously described.




The laundry devices of the present invention can be used with a variety of water-insoluble DTI compounds


29


. These water-insoluble DTI compounds can be provided as a solid, gel, and the like. These DTI compounds can deliver the dye transfer inhibiting benefit by a variety of techniques, including, but not limited to trapping the dye in such a manner that it is unavailable for re-deposition onto a fabric, precipitating out the dye or adsorbing, absorbing or otherwise becoming associated with any extraneous dyes in the wash water. As used herein, the phrase “substantially water insoluble” is intended to mean that the DTI compound has a solubility in deionized water at 20° C. of less than about 1 gm/liter. A substantially water insoluble DTI compound may comprise a water-soluble dye transfer inhibiting agent which is bound to a water insoluble carrier, or it may comprise a dye transfer inhibiting agent which in itself is water insoluble. Water insoluble carriers for water soluble polymeric agents include inorganic materials such as zeolites, clays such as kaolinites, smectites, hectorite types, silicas (or other detergent ingredients). Additionally, organic water-insoluble materials such as fatty alcohols, esters of fatty acids, or polysaccharides that can form water-insoluble gels upon hydration (e.g. gellan gum, carrageenan gum, agarose etc.) can be used as carriers herein. For the dye transfer inhibiting agents which are themselves water insoluble, water insolubility can be achieved by cross-linking, either starting from the known water soluble dye transfer inhibiting polymeric agents, or starting from monomers of these polymers. Other compounds that are suitable as water insoluble DTI agents are any compound exhibiting ion exchange properties, preferably anion exchangers. For instance, non-limiting examples of such products are Dowex® exchange resins of the Dow Chemical Co. or equivalent from other suppliers; Sephadex®, Sepharose® or Sephacel® exchange resins all from Pharmacia Biotech; any other polysaccharide having ion exchange properties such as modified cellulosics, starches; other derivatives of the wood industry such as wood pulp or lignin.




Water soluble polymeric dye transfer inhibiting agents that are suitable to be bound to insoluble carriers, or to be made insoluble via cross-linking are those polymers known in the art to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash. Especially suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, polymers and copolymers of N-vinylpyrrolidone and N-vinylimidazole, vinyloxazolidones, vinylpyridine, vinylpyridine N-oxide, other vinylpyridine derivatives or mixtures thereof.




a) Polyamine N-oxide Polymers




The polyamine N-oxide polymers suitable for use contain units having the following structure formula:











wherein




P is a polymerisable unit, whereto the R—N—O group can be attached to or wherein the R—N—O group forms part of the polymerisable unit or a combination of both.











R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N—O group can be attached or wherein the nitrogen of the N—O group is part of these groups.




The N—O group can be represented by the following general structures:











wherein




R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N—O group can be attached or wherein the nitrogen of the N—O group forms part of these groups.




The N—O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.




Suitable polyamine N-oxides wherein the N—O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N—O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N—O group is attached to the R-group. Other suitable polyamine N-oxides are the polyamine oxides whereto the N—O group is attached to the polymerisable unit. Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N—O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof. Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N—O functional group is attached to said R groups. Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.




Any polymer backbone can be used as long as the amine oxide polymer formed has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of about 10:1 to about 1:1000000. However the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from about 2:3 to about 1:1000000. More preferably from about 1:4 to about 1:1000000, and most preferably from about 1:7 to about 1:1000000. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a pKa<10, preferably pKa<7, more preferred pKa<6. The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerization is not critical provided the material has the desired dye-suspending power. Typically, the average molecular weight is within the range of about 500 to about 1000,000; preferably from about 1,000 to about 50,000, more preferably from about 2,000 to about 30,000, and most preferably from about 3,000 to about 20,000.




b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole




The N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from about 5,000 to about 1,000,000, preferably from about 5,000 to about 200,000. Highly preferred polymers for use in the laundry detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from about 5,000 to about 50,000; more preferably from about 8,000 to about 30,000; and most preferably from about 10,000 to about 20,000. The average molecular weight range was determined by light scattering as described in Barth H. G. and Mays J. W. Chemical Analysis Vol 113,“Modem Methods of Polymer Characterization”. Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from about 5,000 to about 50,000; more preferably from about 8,000 to about 30,000; most preferably from about 10,000 to about 20,000. The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties. The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from about 1 to about 0.2, more preferably from about 0.8 to about 0.3, and most preferably from about 0.6 to about 0.4.




c) Polyvinylpyrrolidone




Polyvinylpyrrolidone (“PVP”) having an average molecular weight from about 2,500 to about 400,000 can also be utilized; preferably from about 5,000 to about 200,000; more preferably from about 5,000 to about 50,000; and most preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, N.Y. and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696).




d) Polyvinyloxazolidone




One may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight from about 2,500 to about 400,000; preferably from about 5,000 to about 200,000; more preferably from about 5,000 to about 50,000; and most preferably from about 5,000 to about 15,000.




e) Polyvinylimidazole




One may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight from about 2,500 to about 400,000; preferably from about 5,000 to about 200,000; more preferably from about 5,000 to about 50,000; and most preferably from about 5,000 to about 15,000.




f) Cationic Polymers




Such polymers are those having a cationic group into their polymeric backbone, as shown by the formula:











Wherein P represents polymerisable units, Z represents alkyl or aryl groups, oxygen or ester, ether, amide, amine group, Cat represents cationic groups, preferably including quaternized N groups or other cationic units, x=0 or 1, y=0 or 1, t=0 or 1. Preferred cationic polymers are quaternized polyvinylpyridines.




Water insolubility can, in the case of non-cross linked polymers, also be achieved by selecting very high molecular weight range, or by copolymerizing, or by varying the degree of oxidation if appropriate, depending on the polymer. Polymers which are water soluble, such as those described in U.S. Pat. No. 5,912,221, may be made insoluble if the molecular weight is increased above 400,000.




g) Cross-linked Polymers




Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups on the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039. In one embodiment, the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure. In another embodiment, the cross-linked polymers entrap the dyes by swelling. Such cross-linked polymers are described in U.S. Pat. No. 5,912,221.




Thus, a cross-linked polymer has one or more individual molecular chains linked by side branches to adjacent chains. The cross-links can be formed: (a) between already existing linear or branched polymers, (b) during the polymerization of multi-functional monomers, or (c) during the polymerization of dimeric monomers with traces of multi-functional monomers. The cross-linking can also be achieved by various means known in the art. For instance, the cross-links can be formed using radiation, oxidation and curing agents, such as divinylbenzene, epichlorohydrin and the like. Preferably, cross-linked polymers for the purpose of this invention are those obtained by cross-linking a water-soluble dye tranfer inhibiting polymer described above with divinylbenzene (DVB) cross-linking agent during polymerisation of the DTI monomer. Cross-linking degree can be controlled by adjusting the amount of divinylbenzene (DVB) cross-linking agent. Preferably, the degree of cross-linking is between about 0.05% (w/w) of DVB over DTI monomer and about 50% of DVB over DTI monomer and, more preferably, between about 0.05%(w/w) of DVB over DTI monomer and about 25%(w/w) of DVB over DTI monomer. Most preferably, the degree of cross-linking is between about 0.1%(w/w) of DVB over DTI monomer and about 5%(w/w) of DVB over DTI monomer. The cross linking forms DTI compound particles, at least 90% (and more preferably at least about 95%) of which have a minimum diameter as measured by conventional methods for particle size distribution evaluation of at least about 1 μm, preferably at least about 50 μm, and more preferably at least about 75 μm, all as measured in their dry state. Most preferably, the cross linking forms DTI compounds, at least 90% (and more preferably at least about 95%) of which have a minimum diameter as measured by conventional methods for particle size distribution evaluation of between about 1 μm and about 5 mm, still more preferably between about 50 μm and about 2500 μm, and yet still more preferably between about 75 μm and about 1500 μm, all as measured in their dry state. Preferably, the cross-linked polymer is a polyamine N-oxide or a quaternized polyamine. The skilled in the art may conveniently obtain such compounds by oxidizing or quaternizing cross-linked polyvinylpyridines from Reilly Industries Inc. commercialized under the name Reillex™ 402 or Reillex™ 425 by methods known in the art. For instance, but not exclusively, the method described in U.S. Pat. No. 5,458,809 can be used to prepare a polyamine N-oxide of interest from the commercially available compounds given above. An example of quaternized polyamine can also be obtained from Reilly Industries under the commercial name Reillex™ HPQ.




The laundry devices of the present invention are used in the same manner as conventional laundry dosing and dispensing devices known in the art. In other words, the subject laundry devices (e.g., a bag or a bag in combination with a container storing a laundry product) can be placed directly in the wash water prior to the start of a wash cycle or can be attached or suspended to the interior of a washing machine tub. The laundry devices of the present invention can also be stored within a package, such as a carton, shipping container, or other article of manufacture, having instructions in association therewith for using the laundry device to deliver a dye transfer inhibiting benefit to the wash water. As used herein, the phrase “in association with” is intended to refer to refer to instructions that are either directly printed on the package or container itself or presented in a different manner including, but not limited to, a brochure, print advertisement, electronic advertisement, audio, audio-visual, and the like, so as to communicate the set of instructions to a consumer of the article of manufacture. For example, the set of instructions could comprise the following steps for delivering a dye transfer inhibiting benefit to the wash water:




1. For a bag stored within a package, either:




(a) placing the bag directly in the wash water or attaching it to the drum or the agitator of the washing machine, or




(b) assembling the bag with a container, filling the container with a laundry product, and placing the combination of the bag and container in the wash water;




2. For a bag and container stored within a package,




(a) assembling the bag with a container; and




(b) filling the container with a laundry product, and placing the combination of the bag and container in the wash water.




DYE REMOVAL TEST METHOD




The following procedure is useful for characterizing the dye removal efficiency of the water-insoluble DTI compounds and materials forming the bags storing these compounds which are made in accordance with the present invention. Specific units may be suggested in connection with measurement and/or calculation of parameters described in the procedures. These units are provided for exemplary purposes only. Other units consistent with the intent and purpose of the procedures can be used.




Three glass marbles and 2.4 g of the detergent composition set forth in Table 1 are added to a Launder-O-Meter pot meeting the requirements of ISO 105-C01-6. For DTI compounds that are incompatible with anionic surfactants such as cationic polymers described under f) above, fully nonionic detergent compositions may also be used to assess dye removal efficiency. Exemplary Launder-O-Meter and pots are the Washtec series which are manufactured by Roaches Engineering, Inc. of the United Kingdom for wash and dry clean fastness testing.















TABLE 1











Ingredient




% (w/w)



























Sodium linear alkylbenzene sulfonate




15







Alcohol ethoxylate




10







Sodium citrate (as citric acid)




1







Soap (as free fatty acid)




10







Propane diol




9







Ethanol




2







Monoethanolamine (adjust to pH 7.8-8.0)




7







Silicone antifoam agent




0.5







Demineralized water




Balance















The pot solution is brought to 300 mL by adding an appropriate amount of demineralized water. To this pot solution is added 1.33±0.01 mL. of a solution of direct blue 1 dye at 2.27 mM concentration (˜0.225% w/w). This yields an absorbance as defined by Beer's law of about 0.70 at 620 nm. A 5 cm wide×5 cm long bag, which is made from the subject apertured material (i.e., the apertured material to be tested), containing 1.00±0.01 g of the subject water-insoluble DTI compound (i.e., the DTI compound to be tested), is added to the pot.




The pot containing the dye solution, the DTI bag and the detergent composition is agitated for 0.50±0.02 hours at 40.0±2.0° C. in the Launder-O-Meter. After 0.5 hours, the bag is immediately removed and rinsed thoroughly. The pot solution is filtered after cooling to room temperature over a 0.5 μm filter to remove any matter in suspension and the residual absorbance of the dye solution is measured at 620 nm. Repeat the operation 15 times, using the same bag containing the same DTI compound but using a fresh dye solution aliquot and a fresh detergent dose at each cycle throughout the test. The absorbance values at 620 nm versus the initial absorbance of the untreated dye solution at the same wavelength reflect the ability of the DTI bag to remove the dye from the wash solution over repeated exposure to dye in solution, in the presence of a laundry detergent. Dye removal efficiency is calculated from the following equation:







%
Removal

=


(

1
-


Absorbance





at





Cycle





n


Initial





Absorbance



)






100











According to this test method, substantially water-insoluble DTI compounds and apertured materials made in accordance with the present invention have a Dye Removal Efficiency of at least about 10% dye removal after 15 test wash cycles and preferably at least about 25% dye removal after 15 test wash cycles. Most preferably, laundry devices of the present invention achieve at least about 50% dye removal after 15 test wash cycles.




The following is an illustrative example of application of the Dye Removal Test Method:




EXAMPLE 1




A water-insoluble DTI compound comprising cross-linked polyvinylpyridine N-oxide (0.5% divinylbenzene cross-linking degree) is placed in a spunbonded polypropylene non-woven material of 60 gr/m


2


weight. The initial absorbance of the dye at 620 nm is measured to be 0.71±0.01 as previously described. After completing the above-described 15 cycles, the dye absorbance at 620 nm is measured to be 0.16±0.01. Therefore, the subject substantially water insoluble DTI compound and apertured material have a Dye Removal Efficiency of about 77% dye removal after 15 test wash cycles.




The foregoing description of the preferred embodiments of the invention have been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Modifications or variations are possible and contemplated in light of the above teachings by those skilled in the art, and the embodiments discussed were chosen and described in order to best illustrate the principles of the invention and its practical application. It is intended that the scope of the invention be defined by the claims appended hereto.



Claims
  • 1. A laundry device for use with a washing machine, comprising:a water-insoluble dye transfer inhibiting compound selected from the group consisting essentially of polyvinylpyridine N-oxide, quaternized polyvinylpyridine, polyvinylpyrrolidone, poly(vinylpyrrolidone-co-vinylimidazole), and mixtures thereof, wherein said water-insoluble dye transfer inhibiting compound has an average particle size of at least about 75 μm; and a bag storing said water-insoluble dye transfer inhibiting compound, wherein at least a portion of said bag is formed from a material having a plurality of apertures allowing wash water to flow through said bag but substantially preventing said water-insoluble dye transfer inhibiting compound from exiting said bag during use.
  • 2. The laundry device of claim 1, wherein said water-insoluble dye transfer inhibiting compound is cross linked and wherein the degree of said cross-linking is obtained with amounts of cross-linking agent between about 0.05% and about 25% by weight dye transfer inhibiting monomer.
  • 3. The laundry device of claim 1, wherein said water-insoluble dye transfer inhibiting compound is a water-soluble dye transfer inhibiting polymer bound to a water-insoluble carrier.
CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No. 09/431,552 to MASSCHELEIN et al, filed Oct. 29, 1999 (P&G Case 7842) and now U.S. Pat. No. 6,410,496.

US Referenced Citations (8)
Number Name Date Kind
4380453 Claiborne Apr 1983 A
4494264 Wattiez et al. Jan 1985 A
4835804 Arnau-Munoz et al. Jun 1989 A
4969927 Schumann et al. Nov 1990 A
5698476 Johnson et al. Dec 1997 A
5881412 Ziskind Mar 1999 A
5912221 Van Leeuwen et al. Jun 1999 A
6035473 Felstead et al. Mar 2000 A
Foreign Referenced Citations (6)
Number Date Country
0 719 856 Jul 1996 EP
1 026 231 Aug 2000 EP
2761702 Oct 1998 FR
1 356 642 Jun 1974 GB
WO 9620996 Jul 1996 WO
WO 9626831 Sep 1996 WO
Continuations (1)
Number Date Country
Parent 09/431552 Oct 1999 US
Child 10/170792 US