EP1345524B1 - Verbessertes Reinigungsgerät mit abnehmbarem Erhöhungselement - Google Patents

Verbessertes Reinigungsgerät mit abnehmbarem Erhöhungselement Download PDF

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Publication number
EP1345524B1
EP1345524B1 EP01995146A EP01995146A EP1345524B1 EP 1345524 B1 EP1345524 B1 EP 1345524B1 EP 01995146 A EP01995146 A EP 01995146A EP 01995146 A EP01995146 A EP 01995146A EP 1345524 B1 EP1345524 B1 EP 1345524B1
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EP
European Patent Office
Prior art keywords
cleaning
pad
cuff
mop head
layer
Prior art date
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Expired - Lifetime
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EP01995146A
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English (en)
French (fr)
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EP1345524A2 (de
Inventor
Nicola John Policicchio
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of EP1345524A2 publication Critical patent/EP1345524A2/de
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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/20—Mops
    • A47L13/24—Frames for mops; Mop heads
    • A47L13/254—Plate frames

Definitions

  • the present invention relates to cleaning implements and cleaning sheets particularly suitable for removal and entrapment of dust, lint, hair, sand, food crumbs, grass and the like.
  • cleaning implement for cleaning hard surfaces such as mops
  • Such mops typically comprise a handle connected to a mop head which engages a cleaning sheet and the user then wipes the mop against the floor to be cleaned.
  • Those mop heads have typically a flat surface at the bottom.
  • wet cleaning where a liquid is either sprayed on the surface to be cleaned or is already included in a cleaning pad, those mops do not allow a very good usage of the pad. It has been shown that only the front part of the pad which is first in contact with the liquid and where most of pressure exercised by the user is concentrated, is actually contributing to the cleaning.
  • the present invention relates to a cleaning implement for hard surface cleaning comprising:
  • the term “comprising” means that the various components, ingredients, or steps, can be conjointly employed in practicing the present invention. Accordingly, the term “comprising” encompasses the more restrictive terms “consisting essentially of” and “consisting of.”
  • direct fluid communication means that fluid can transfer readily between two cleaning pad components or layers (e.g., the scrubbing layer and the absorbent layer) without substantial accumulation, transport, or restriction by an interposed layer.
  • tissue, nonwoven webs, construction adhesives, and the like can be present between the two distinct components while maintaining "direct fluid communication", as long as they do not substantially impede or restrict fluid as it passes from one component or layer to another.
  • the term "macroscopically expanded" when used to describe three-dimensional plastic webs, ribbons, and films refers to webs, ribbons, and films which have been caused to conform to the surface of a three-dimensional forming structure so that both surfaces thereof exhibit the three-dimensional pattern of said forming structure, said pattern being readily visible to the naked eye when the perpendicular distance between the viewer's eye and the plane of the web is about 30,48 cm (12 inches).
  • Such macroscopically expanded webs, ribbons and films are typically caused to conform to the surface of said forming structures by embossing, i.e., when the forming structure exhibits a pattern comprised primarily of male projections, by debossing, i.e., when the forming structure exhibits a pattern comprised primarily of female capillary networks, or by extrusion of a resinous melt directly onto the surface of a forming structure of either type.
  • the term "planar”, when utilized herein to describe plastic webs, ribbons and films refers to the overall condition of the web, ribbon or film when viewed by the naked eye on a macroscopic scale.
  • planar webs, ribbons and films can include webs, ribbons and films having fine scale surface aberrations on one or both sides, said surface aberrations not being readily visible to the naked eye when the perpendicular distance between the viewer's eye and the plane of the web is about 30,48 cm (12 inches) or greater.
  • z-dimension refers to the dimension orthogonal to the length and width of the cleaning pad of the present invention, or a component thereof. The z-dimension therefore corresponds to the thickness of the cleaning pad or a pad component.
  • the term "x-y dimension" refers to the plane orthogonal to the thickness of the cleaning pad, or a component thereof.
  • the x and y dimensions correspond to the length and width, respectively, of the cleaning pad or a pad component.
  • the implement will be moved in a direction parallel to the y-dimension (or width) of the pad.
  • the present invention is not limited to cleaning pads having four sides. Other shapes, such as circular, elliptical, and the like, can also be used.
  • the term “layer” refers to a member or component of a cleaning pad whose primary dimension is x-y, i.e., along its length and width. It should be understood that the term layer is not necessarily limited to single layers or sheets of material. Thus a layer can comprise laminates or combinations of several sheets or webs of the requisite type of materials. Accordingly, the term “layer” includes the terms “layers” and “layered.”
  • hydrophilic is used to refer to surfaces that are wettable by aqueous fluids deposited thereon. Hydrophilicity and wettability are typically defined in terms of contact angle and the surface tension of the fluids and solid surfaces involved. This is discussed in detail in the American Chemical Society publication entitled Contact Angle, Wettability and Adhesion, edited by Robert F. Gould (Copyright 1964 ). A surface is said to be wetted by a fluid (i.e., hydrophilic) when either the contact angle between the fluid and the surface is less than 90°, or when the fluid tends to spread spontaneously across the surface, both conditions normally co-existing. Conversely, a surface is considered to be “hydrophobic” if the contact angle is greater than 90° and the fluid does not spread spontaneously across the surface.
  • the term "scrim” means any durable material that provides texture to the surface-contacting side of the cleaning pad's scrubbing layer, and also has a sufficient degree of openness to allow the requisite movement of fluid to the absorbent layer of the cleaning pad.
  • Suitable materials include materials that have a continuous, open structure, such as synthetic and wire mesh screens. The open areas of these materials can be readily controlled by varying the number of interconnected strands that comprise the mesh, by controlling the thickness of those interconnected strands, etc.
  • Other suitable materials include those where texture is provided by a discontinuous pattern printed on a substrate.
  • a durable material e.g., a synthetic
  • a continuous or discontinuous pattern such as individual dots and/or lines
  • the continuous or discontinuous pattern can be printed onto a release material that will then act as the scrim.
  • These patterns can be repeating or they can be random. It will be understood that one or more of the approaches described for providing the desired texture can be combined to form the optional scrim material.
  • the z direction height and open area of the scrim and or scrubbing substrate layer help to control and or retard the flow of liquid into the absorbent core material.
  • the z height of the scrim and or scrubbing substrate help provide a means of controlling the volume of liquid in contact with the cleaning surface while at the same time controlling the rate of liquid absorption, fluid communication into the absorption core material.
  • an "upper" layer of a cleaning pad is a layer that is relatively further away from the surface that is to be cleaned (i.e., in the implement context, relatively closer to the implement handle during use).
  • the term “lower” layer conversely means a layer of a cleaning pad that is relatively closer to the surface that is to be cleaned (i.e., in the implement context, relatively further away from the implement handle during use).
  • the scrubbing layer is preferably the lower-most layer and the absorbent layer is preferably an upper layer relative to the scrubber layer.
  • the terms "upper” and “lower” are similarly used when referring to layers that are multi-ply (e.g., when the scrubbing layer is a two-ply material).
  • a first layer is a “lower” layer relative to a second layer.
  • a third layer is an “upper” layer relative to a second layer.
  • the terms “above” and “below” are used to describe relative locations of two or more materials in a cleaning pad's thickness.
  • a material A is “above” material B if material B is positioned closer to the scrubbing layer than material A.
  • material B is “below” material A in this illustration.
  • the present invention is used in combination with hard surface cleaning compositions, preferably for use with the cleaning pads and/or cleaning implements described herein, comprising:
  • the present invention is used in synergy with a cleaning pad, preferably disposable, for cleaning a hard surface, the cleaning pad comprising:
  • the improved cleaning implement is used in synergy with a cleaning sheet, preferably disposable, for cleaning hard surfaces, the cleaning sheet comprising functional cuffs, preferably free-floating, double-layer loop functional cuffs.
  • an important aspect of cleaning performance is related to the ability to provide a cleaning pad having apertured formed films, a liquid impervious attachment layer, and/or density gradients, and/or functional cuffs and a cleaning sheet having functional cuffs.
  • a typical cleaning operation i.e., where the cleaning pad and/or sheet is moved back and forth in a direction substantially parallel to the pad's or sheet's y-dimension or width
  • each of these structural elements provide the cleaning pads and/or sheets improved cleaning performance, both separately and in combination with one or more additional elements.
  • Apertured formed films are pervious to liquids and provide efficient transfer of liquid from the surface being cleaned to other layers of the cleaning pad, preferably one or more absorbent layers, while reducing the tendency for such liquid to be squeezed back onto the surface being cleaned.
  • Functional cuffs are preferably free-floating so as to "flip" back and forth in the y-dimension during a typical cleaning operation, thus trapping particulate matter and reducing the tendency for such particulate matter to be redeposited on the surface being cleaned.
  • Density gradients are preferably incorporated in the absorbent layer(s) of the cleaning pad to "pump" or "wick” liquid away from the surface being cleaned to areas in the cleaning pad furthest away from the surface being cleaned.
  • the liquid impervious attachment layer provides a barrier which helps to better distribute the liquid in the x-y direction after liquid reaches the back of the pad which is further set away from cleaning surface.
  • the absorbent layer In the case of drapers, sanitary napkins, incontinence devices, and the like, the absorbent layer typically needs to handle only liquids with dissolved components, such as bodily fluids. Second, the absorbent layer of a cleaning pad needs to absorb liquid against the force of gravity. In terms of diapers, sanitary napkins, incontinence devices, and the like, the absorbent layer typically has the force of gravity to pull liquid into, and distribute it throughout, the absorbent layer. Having sufficient resiliency in the cleaning pad is important, as described below, in maintaining good cleaning performance, especially in cleaning pads comprising a density gradient.
  • the preferred cleaning pads comprising the specific density gradients described herein exhibit improvements in at least three important characteristics affecting hard surface cleaning performance: acquisition (the time required to transfer liquid from the surface being cleaned to the absorbent layer(s) of the cleaning pad), distribution (the liquid wicking ability of the absorbent layer(s) so as to utilize as much of the pad as possible), and rewet (the amount of dirty liquid retained within the absorbent layer(s) and not squeezed out during a cleaning process).
  • the absorbent layer can comprise a single absorbent layer with a continuous density gradient in the cleaning pad's z-dimension, or multiple absorbent layers having different densities resulting in a density gradient.
  • a continuous density gradient is one in which the material comprising the cleaning pad is homogeneous, but has differing densities throughout the material.
  • a process for creating a continuous density gradient is disclosed in U.S. Patent No. 4,818,315, issued April 4, 1989 to Hellgren et al ..
  • the cleaning pad used in combination with the present invention comprises a density gradient resulting from multiple absorbent layers, preferably three, each having a different density.
  • a density gradient is typically "strong" when the density of the absorbent layers increase from a lower absorbent layer to an upper absorbent layer.
  • the present cleaning pads comprise a "strong" density gradient, which provides fast acquisition, better core utilization by effectively wicking liquid in the z- and x-y directions, and a reduced tendency for allowing absorbed liquids, especially those containing undissolved particulate, to be squeezed out.
  • a strong density gradient preferably comprises at least two absorbent layers, with a first absorbent layer having a density of from about 0.01 g/cm 3 to about 0.15 g/cm 3 , preferably from about 0.03 g/cm 3 to about 0.1 g/cm 3 , and more preferably from about 0.04 g/cm 3 to about 0.06 g/cm 3 , and a second absorbent layer having a density of from about 0.04 g/cm 3 to about 0.2 g/cm 3 , preferably from about 0.1 g/cm 3 to about 0.2 g/cm 3 , and more preferably from about 0.12 g/cm 3 to about 0.17 g/cm 3 ; wherein the density of the first absorbent layer is about 0.04 g/cm 3 , preferably about 0.07 g/cm 3 , and more preferably about 0.1 g/cm 3 , less than the density of the second absorbent layer.
  • the present cleaning pad comprises a density gradient resulting from three absorbent layers, wherein a first absorbent layer has a density of from about 0.01 g/cm 3 to about 0.08 g/cm 3 , preferably from about 0.03 g/cm 3 to about 0.06 g/cm 3 , and a second absorbent layer has a density of from about 0.03 g/cm 3 to about 0.12 g/cm 3 , preferably from about 0.07 g/cm 3 to about 0.1 g/cm 3 , and a third absorbent layer has a density of from about 0.05 g/cm 3 to about 0.2 g/cm 3 , preferably from about 0.08 g/cm 3 to about 0.15 g/cm 3 ; wherein the difference in density between the first absorbent layer and the second absorbent layer, and between the second absorbent layer and the third absorbent layer, is at least about 0.02 g/cm 3 , preferably at least about 0.04 g/cm
  • the cleaning pad comprises a first absorbent layer having a density of about 0.05 g/cm 3 , a second absorbent layer having a density of about 0.1 g/cm 3 , and a third absorbent layer having a density of about 0.15 g/cm 3 . It is recognized that a such a density gradient can be present in a cleaning pad with or without layers having multiple widths in the z-dimension.
  • the porosity meaning the ratio of the volume of interstices of a material to the volume of its mass, of the absorbent layer will typically decrease as the density increases.
  • the porosity is important, particularly in the context of a cleaning pad for cleaning hard surfaces, because the liquid to be absorbed by the cleaning pad typically contains moderate amounts of relatively large particulate matter.
  • the larger particulate matter becomes entrapped in the interstices of the lower absorbent layers.
  • the porosity of the absorbent layers decreases, and the density increases, the larger particulate matter becomes trapped in the larger interstices of the lower absorbent layers and the remaining liquid is then transferred to the upper absorbent layers.
  • the cleaning pad retains both liquid and particulate matter much more effectively than cleaning pads without a strong density gradient.
  • an absorbent layer has a density of less than about 0.1 g/cm 3
  • the layer tends to be less resilient, which is another important property of the present cleaning pad as discussed below.
  • a thermoplastic material preferably a bicomponent fiber
  • an absorbent layer having a density of less than about 0.05 g/cm 3 preferably comprises at least about 20%, preferably at least about 30%, more preferably at least about 40%, of a thermoplastic material such as a bicomponent fiber.
  • a preferable bicomponent fiber comprises a copolyolefin bicomponent fiber comprising a less than about 81% polyethylene terphthalate core and a less than about 51% copolyolefin sheath and is commercially available from the Hoechst Celanese Corporation under the tradename CELBOND ® T-255.
  • one aspect of the present invention is directed to a mop for use with a removable cleaning sheet or cleaning pad which is attached to a mop head having a resilient bottom surface, a portion of which preferably has a substantially stepped profile which engages the removable cleaning pad. While the present invention is discussed herein with respect to a floor mop for purposes of simplicity and clarity, it will be understood that the present invention can be used with other types of mops and cleaning implements which have a cleaning sheet or pad releasably secured there about.
  • the floor mop 20 comprises a mop head 22 having a leading edge 24 and a trailing edge 26.
  • leading edge is intended to refer to the furthest edge of the mop head 22 which leads the mop head 22 when it is moved in a forward direction away from its user.
  • trailing edge is intended to refer to the furthest edge of the mop head 22 which trails the mop head 22 when it is moved in a forward direction away from its user.
  • the leading edge 24 and the trailing edge 26 are substantially parallel to the longitudinal axis 28 of the mop head 22, as shown in Fig 1, wherein the longitudinal axis 28 is the axis along the length of the mop head 22.
  • a pivotable joint such as the universal joint 30, interconnnects the handle 32 of the mop 20 with the mop head 22.
  • the universal joint 30 comprises two rotational axes which allow the handle 32 to pivot in directions 36 and 38.
  • the handle 32 is threadably interconnected with the universal joint 30 at the connection 40.
  • the handle 32 can be provided as a unitary structure or can comprise three sections 34, 36, and 38 which are threadedly interconnected with each other so that the floor mop 20 can be shipped within a carton of convenient size and later assembled for use.
  • the handle section 38 can be provided with an elastic and resilient portion suitable for gripping by a user of the floor mop 20.
  • the mop head 22 also comprises a plurality of attachment structures 42.
  • the attachment structures 42 are configured to receive and retain a cleaning sheet or pad 44 about the mop head 22, as shown in Fig. 2, during use.
  • the attachment structures 42 are preferably disposed at the corners of the mop head 22, although these locations can be varied depending upon the size and shape of the mop head 22.
  • the attachment structures 42 are preferably provided in the form described in copending US application no. 09/364,714, filed August 13, 1999 , naming Kingry et al. as joint inventors.
  • the floor mop 20 is preferably used in combination with the disposable cleaning sheet 44 which is releasably attached to the mop head 22 using the slitted attachment structures 42.
  • the mop 20 comprises a handle 32, a support bead or mop head 22 attached to the handle by a universal joint 30, and a container 34 in fluid communication with a liquid delivery system which includes at least a spray nozzle 25 preferably attached to the mop head 22, one such arrangement being described in U.S. patent no. 5,888,006 to Ping et al., issued March 30,1999 .
  • the cleaning sheet or pad can be provided in the form of a woven or non-woven fabric capable of uniformly absorbing a liquid or having gradient of density of absorption, as discussed more fully hereafter.
  • a pad 48 having a stepped design and which can be adhesively attached to the base of a mop head 22 is illustrated.
  • a stepped design pad comprising two elevational elements 148 and 248 is illustrated.
  • a stepped design pad comprising three elevational elements 148, 248 and 348 is illustrated.
  • the present invention is not limited to stepped design pads comprising two or three elevational elements.
  • stepped design pads may offer similar benefits such as for instance a stepped design comprising a single elevational element or a stepped design comprising more than three elevational elements.
  • the bottom surface of the pad 48 engages at least a portion, and, more preferably, a substantial portion of the cleaning sheet 44 during use, as shown in Fig. 5.
  • the bottom surface of the pad 48 is provided with a profile shape, profile size, and gap which produces a repeated rocking motion of the mop head during use.
  • the width 153 of the contact surface 152 provides a mop which can repeatedly "rock” or “pivot” or “rotate” about the contact surface 152 during any single continuous forward and/or backward sweeping motion of the mop 20, thereby increasing the surface of the cleaning sheet or pad 44 contacting with the dirt directly on the floor or in case of "wet cleaning" the liquid sprayed on the floor.
  • this rocking motion enables collection across a larger percentage of the surface area of the cleaning sheet 44 as the bottom surface of the sheet repeatedly engages and disengages the hard surface to be cleaned due to the rocking motion.
  • contact surface is intended to refer the portion of the cross-sectional profile of the bottom surface of either the mop head 22 or the cleaning sheet 44 contacted by a straight line 56 tangent to the apex of that bottom surface, wherein the straight line 56 is substantially perpendicular to the transverse axis 58 of the mop head 22.
  • the stepped design pad is obtained by attaching at least one elevational element 148 to the pad 48 with fasteners such as adhesive, double faced adhesive tape, Velcro® or any other fasteners know in the art.
  • the stepped design can also be obtained by molding the elevational element directly during the molding process of the pad 48 or the molding process of the mop head 22 such that it is permanently built in.
  • the width of the elevational element is smaller than the width of the mop head.
  • the elevational element is centered on the mop head such that the mop head is equally capable of pivoting forward and backward.
  • the stepped shape is obtained by attaching or molding a plurality of elevational element to the mop head.
  • those elevational elements can be squared, rounded, angled, textured or any combination thereof.
  • the surface 152, 252, and 352 etc... of those elevational elements, which is facing the floor to be cleaned, is generally flat but a surface having discontinuities may be used with the same benefits. For instance, such discontinuities could be in the form of a grid, bumps or holes but other sorts of discontinuities might be used with the same benefits.
  • the elevational elements can be made of a variety of material having different properties. For instance, those elevational elements can all be made of a material which is generally non-deformable.
  • all the elevational elements can be made of a material which is generally deformable, such as foams, sponges, polyester wadding, encased gels or liquids and the like.
  • Deformable materials would be defined as any materials that temporarily lose their shape under normal mopping pressures (0.6895 to 1.379 kPa (about 0.1 to 0.2 psi)) but which retrieve their original shape when pressure is relieved.
  • the use of more deformable materials used to form the elevational clement can also be beneficial by creating a pumping action improving liquid uptake as the absorbent pad is wiped across the surface, by improving rocking action, since such materials are more easily deformable as the implement is wiped in an back and forth motion and by providing cushioning which can protect the floor surface from possible damage and make wiping easier especially when thinner pads are used or cleaning pads which have an absorbent core narrower than the width of the mop head or dusting sheets.
  • a combination of generally non-deformable and deformable material can be used for different elevational elements. This combination of elevational elements made of material having different properties may increase or improve the ability of the mop head to pivot relative the surface to be cleaned.
  • the mop head 22 and universal joint 26 are preferably formed from ABS type-polymers (e.g., terpolymer from acrylonitrile), polypropylene or other plastic material by injection molding.
  • the stepped design pad 48 and each individual elevational element can be formed from polyurethane by molding or from ABS type-polymers (e.g., terpolymer from acrylonitrile), polypropylene or other plastic material by injection molding.
  • the mop handle 32 can be formed from aluminum, plastic, or other structural materials.
  • US Patent 6,101,661 to Policicchio et al. disclosed a cleaning pad comprising multiple planar surfaces contacting the surface to be cleaned.
  • the thickness of all the layers forming the absorption substrate is sufficient to generate the desired rocking motion.
  • the combination of this cleaning pad with the improved cleaning implement will provide further improvement and/or allow optimization of the pad where the pad could be made thinner and/or less absorbent. Making the cleaning pad thinner and less absorbent is particularly useful in creating what would be referred to as a "light duty" pad.
  • a light duty pad is beneficial for consumers with smaller homes who have less area to clean.
  • absorptive capacity is defined as the maximum amount of solution a pad can uptake before it is exhausted. While there are benefits to creating a "light duty" pad, reducing the absorbent capacity and making the pad thinner can substantially affect the way this cleaning pad functions and performs. For example reducing the absorptive capacity results in lower "absorptive efficiency" - which is defined as the amount of solution a pad can uptake at a given amount of solution dosing and a given amount of contact time with the solution. In addition, as the pad is made thinner the "rocking action" during mopping is reduced.
  • Tests is done on both ceramic and pre-finished wood floors to measure under different floor quality conditions. The different results obtained can be explained in part by different "wetability" of the surfaces and by the fact that the ceramic tiles used in this test have grout lines (6 mm wide X 3 mm deep) where solution can settle and make it more difficult for a cleaning pad to absorb since the contact between the cleaning pad and the surface is reduced.
  • the test area is composed of 5 X 1 sqm test surfaces of tile and 5 X 1 sqm area of finished wood.
  • a mop head with a flat pad and a mop head with a stepped design pad are each tested in combination with a two different "Standard Cleaning Pad" having different characteristics and one "Light Duty cleaning Pad.
  • the stepped design pad comprises one elevational element which is attached with adhesive substantially in the center of the bottom of the mop head.
  • the actual dimensions of the elevational element are 25 mm wide by 265 mm long by 1 mm high.
  • This elevational element is attached to the bottom of a mop head which is 114 mm wide by 265 mm long.
  • the flat mop head has the same dimension than the stepped design mop head to the extent it does not include an elevational element.
  • This test was performed with standard cleaning pads comprising 3 absorbent layers having different width, length and thickness.
  • the first and second standard pad also comprise different pairs of "looped” functional cuffs.
  • the "light duty” cleaning pad comprises two absorbent layers and a pair of “looped” functional cuffs similar to those used with the second "standard cleaning pad".
  • the pair of functional cuffs used with the second standard pad and the light duty pad will be described in greater details hereinafter.
  • the absorptive efficiency is calculated by determining the ratio of the amount of the solution absorbed by the cleaning pad relative to the 50 mils applied to floor and then multiplied by 100 to convert it into a percentage.
  • Fig. 6 which shows where the dirty solution Ds is absorbed on a cleaning pad tested with a flat mop head
  • Fig. 7 which shows where the dirty solution Ds is absorbed on a cleaning pad tested with a stepped design mop head.
  • the different layers of absorbent material forming the cleaning pads create a density gradient in the center area of the pads. As a result, those cleaning pads absorb more towards the center area.
  • the stepped design mop head optimizes liquid uptake through the center area of the pad since the solution sprayed on the floor is forceably absorbed through the center portion of the cleaning pad and move in the z direction and the x y direction to make optimum use of the density gradient as illustrated in Fig. 8 and Fig. 9.
  • FIG. 8 shows the solution movement Sm into a cleaning pad comprising three absorbent layers (the upper one having a high density Hd and the lower one having a low density Ld) used with a flat mop head.
  • Fig. 9 shows the solution movement Sm into a cleaning pad also comprising three absorbent layers (the upper one having a high density Hd and the lower one having a low density Ld) used with a stepped design mop head.
  • the point of absorbency is shifted towards the leading edge of the cleaning pad and the benefit of having a density gradient in the pad is significantly reduced.
  • An important feature of the preferred cleaning pads and/or sheets used in synergy with the present invention is the inclusion of one or more improved functional cuffs.
  • functional cuff(s) improve the cleaning performance of traditional cleaning pads and sheets, as well as the cleaning pads and sheets of the present invention.
  • Functional cuffs provide improved particulate pick-up for traditional cleaning pads and sheets, as well as the cleaning pads and sheets of the present invention.
  • FIG. 10 is a perspective view of a cleaning pad 200 comprising a free-floating, looped functional cuff 207.
  • the looped functional cuff 207 has two surfaces 209 and 211.
  • the cleaning pad 200 is moved forward in the Y f direction, then backward in the Y b direction across the surface being cleaned.
  • the functional cuff 207 will flip such that its surface 211 is in contact with the surface being cleaned. Particulate matter on the surface being cleaned is picked-up by the surface 211 of the functional cuff 207.
  • the functional cuff 207 When the cleaning pad 200 is then moved in the Y b direction, the functional cuff 207 will then flip over such that its other surface 209 is in contact with the surface being cleaned. The particulate matter initially picked-up by surface 211 will be trapped between surface 211 of the functional cuff 207 and layer 201 of the cleaning pad 200. Surface 209 of the functional cuff 207 is then capable of picking-up additional particulate matter.
  • Figures 11 and 12 illustrate a cleaning pad 400 comprising two free-floating, looped functional cuffs 411 and 413, similar to the functional cuff 207 in Figure 10.
  • the cleaning pad 400 is moved in the Y f direction across a hard surface and functional cuffs 411 and 413 are flipped such that surfaces 417 and 425 are in contact with the surface being cleaned and are capable of picking-up particulate matter.
  • the cleaning pad 400 is then moved across the hard surface in the Y b direction, causing the functional cuffs 411 and 413 to flip over such that surfaces 419 and 423 are in contact with the surface being cleaned.
  • the particulate matter picked-up by surface 425 is trapped between surface 425 and scrubbing layer 401.
  • Surfaces 419 and 423 are then able to pick-up additional particulate matter from the surface being cleaned.
  • the cleaning pad 400 is moved back across the hard surface in the Y f direction, the additional particulate matter picked-up is trapped between surface 423 and scrubbing layer 401.
  • the height (meaning the z-dimension of a fully-extended functional cuff) of the functional cuff is large enough so that when the functional cuff flips toward the mid-line of the cleaning pad, it overlaps the layer having the narrowest width.
  • Figure 11 shows a cleaning pad 400 comprising two functional cuffs 411 and 413, wherein the functional cuffs 411 and 413 are both flipped toward the mid-line of the cleaning pad, which is preferable for packaging the cleaning pad 400 for resale.
  • the action of the cuffs is schematically illustrated Fig. 13 and 14 showing how large particles Lp are trapped by the cuffs 207 attached to a cleaning pad or sheet 44 when the mop is moved in a forward Yf and backward Yb motion.
  • a cleaning pad and/or sheet comprising functional cuff(s) As a cleaning pad and/or sheet comprising functional cuff(s) is wiped back and forth across a hard surface, the functional cuff(s) "flip" or “roll” from side to side, thus picking-up and trapping particulate matter.
  • Cleaning pads and sheets having functional cuff(s) exhibit improved pick-up and entrapment of larger particulate matter, which are typically found on a hard surfaces, and have a reduced tendency to redeposit such particulate matter on the surface being cleaned.
  • the cuffs play an important role in helping to spread solution and smooth out any lines created by the textures in the floor sheet in order to minimize the formation of streaks during drying.
  • This attribute of helping to spread solution is particular important in the context of a "wet" cleaning implement where the solution is sprayed over a specific concentrated area, often at lower dosing or floor wetness levels compared to conventional systems and then wiped over with an absorbent pad. Since the dosing is low and concentrated to an area covered by the spray pattern width, the pad needs to loosen soil but absorb at a controlled rate. If the pad absorbs too quickly, dry spots will be created during mopping which will lead to streaks from a dry pad wiping across a soiled floor. When the outer part of the cuff is composed of a non-woven material, the cuff is typically able to absorb some liquid between the interstitial spaces between the fibers which make-up the non-woven material.
  • streaks from mopping with a dry pad result from the pad absorbing too quickly particularly when solution dosing is very low or actual spraying of solution is done at a lower frequency intervals (for example, sprayed solution applied every 2 sqm as compared to every 1 ⁇ 2 sqm which is what would be recommended since this is the approximate width typically covered by the spray pattern).
  • the solution spreading attribute provided by the cuff is also further enhanced when the cuff on the leading edge is facing towards the center during the forward mopping motion or the when a cuff on the trailing edge is facing the center during the back mopping motion.
  • the cuff faces the center of the pad it breaks the contact between the floor sheet and the floor over the area covered by the cuff.
  • the portion of the pad covered by the cuff has a reduced absorbing ability since the liquid needs to be absorbed through multiple layers before being able to enter into the core absorbent layer(s)(liquid needs to penetrate through the layers forming the cuff and through potentially the apertured formed film of the cleaning pad).
  • the cuffs play an important role in providing large particulate, hair and lint "trapping" benefits as well as solution spreading. Those characteristics are critical to the overall performance of the cleaning pad. Also as described above, the cuffs optimally function by moving back and forth during the up and down mopping motion. To optimize this ability for the functional cuffs to move back and forth it has been found that the outer cuff characteristics (outer referring to part of cuff that actually contacts floor during mopping) should be different from the inner cuff characteristics (inner referring to part of cuff that rubs against itself during mopping).
  • the inner part of the cuff has a lower friction or "glide” when it rubs against itself as compared to the outer part of the cuff which has a higher friction or “glide” when it rubs against the floor.
  • This differential in friction leads to a different level of force being required to cause the materials to slide or move.
  • the cuffs are better able to freely move back and forth because the force required to break the temporary bond formed between the outer cuff and the floor is easily greater than the force required to break the temporary bond between the inner cuff on itself.
  • Functional cuffs can comprise a variety of materials, including, but not limited to, appertured formed film, carded polypropylene, rayon or polyester, hydroentangled polyester, spun-bonded polypropylene, polyester, polyethlene, or cotton, polypropylene, or blends thereof. Where free-floating functional cuffs are utilized, the material used for the functional cuffs should be sufficiently rigid to allow the cuffs to "flip" from side to side, without collapsing or rolling-over on itself.
  • Rigidity of the functional cuffs can be improved by using high basis weight materials (e.g., materials having a basis weight of greater than about 30 g/m 2 ) or by adding other materials to enhance rigidity such as scrim, adhesives, elastomers, elastics, foams, sponges, scrubbing layers, and the like, or by laminating materials together.
  • the functional cuffs comprise a hydroentangled substrate including, but not limited to, polyester, cotton, polypropylene, and mixtures thereof, having a basis weight of at least about 20 g/m 2 and a scrim material for stiffening.
  • the following testing is conducted to determine which materials exhibit characteristics where the least amount of resistance results when the material is rubbed against itself in both a dry and wet state.
  • a sample of substrate to be tested of 20 cm wide by 30 cm long is prepared. It is then stretched and taped down onto a test surface with the part of the material which would represent the inside part of the cuff facing up. 2. Another sample of the same material is cut into 12 X 12 sqcm. This sample is wrapped and taped around the 6 cm round weight with the part representing the inside of a cuff facing down. 3. With a pen, a mark is made at 2.5 cm in front of back edge of taped down substrate (this represents starting point) and another mark is made at 20 cm forward from the first mark (this represents ending point). 4. The round weight with the wrapped substrate is positioned in front of starting line. The force gauge is attached to the round weight and reads zero.
  • Table 1 Example Material tested on Same Material Dry Glide N (lb.) of force Wet Glide N (lb.) of force (average 3 reps) average 3 reps) 1 20 gsqm apertured formed film (DRI WEAVE film with wide funnel - female side representing the test contact surface) - 3.114 (0.7) 1.112 (0.25) standard deviation.
  • standard deviation 0.2224 (0.05) 0.04448 (0.01) 9 20 gsqm polypropylene carded process 2.891 (0.65) 2.98 (0.67) standard deviation 0.1334 (0.03) 0.04448 (0.01) 10 40 gsqm polyester needle punched - Flow Clean 3.025 (0.68) 3.47 (0.78) standard deviation standard deviation 0.1779 (0.04) 0.1334 (0.03) 11 40 gsqm hydra-entangled polyester- 3.914 (0.88) 3.781 (0.85) standard deviation standard deviation 0.1334 (0.03) 0.2224 (0.05) 12 50 gsqm hydra-entangled polyester one side laminated with 10 gsqm polypropylene scrim facing test surface- 2.98 (0.67) 2.447 (0.55) standard deviation standard deviation 0.1334 (0.03) 0.04448 (0.01) 13 30 gsqm thru-air bond polyester + plyethylene:polyester bicomponent 3.781 (0.85) 3.781 (0.85) standard deviation. standard deviation 0.1334 (0.03) 0.02
  • the following testing is conducted to determine which materials exhibit characteristics where the greatest amount of resistance results when the material is rubbed against a surface (simulating a hard surface to be cleaned) in both a dry and wet state.
  • a smooth, very shiny, glazed ceramic tile is chosen as the test surface since it very slippery.
  • Table 2 Example Material Side Tested on Surface Dry Glide N (lb.) of force Wet Glide N (lb.) of force (average 3 reps) Average 3 reps) 1 20 gsqm apertured formed film (DRI WEAVE film with wide funnel - female side representing test contact surface) 5.338 (1.2) 1.334 (0.3) standard deviation. standard deviation 0 (0) 0.2224 (0.05) 2 20 gsqm apertured formed film (DRI WEAVE film with narrow funnel -male side representing test contact surface) 9.786 (2.2) 3.559 (0.8) standard deviation.
  • standard deviation 0.2224 (0.05) 0.04448 (0.01) 8 20 gsqm polyethylene film 8.896 (2.0) 1.557 (0.35) standard deviation.
  • materials such as those shown in Examples 1, 3,5,6 and 8 provide good characteristics for an inner cuff material because of the low friction as indicated by the low glide values on material to material when tested as inner cuffs shown in Table 1.
  • Preferred materials are typically apertured film with the female side in to form inner cuff in two case of examples 1, 3 and 6 or unapertured film in the case of Examples 8.
  • Alternative materials can be non-woven materials where fibers that have been coated with a high degree of chemical or adhesive coating or binder making the structure smooth such as in Example 5.
  • materials such as those shown in Examples 10, 11, 12 and 13 provide good characteristics for an outer cuff material because of the high friction as indicated by the high glide values when tested as outer cuffs shown in Table 2. These materials are typically non-wovens where the formation process leaves many free fibers. Additionally, the fiber matrix has certain degree of integrity and capillary spaces created by thermal bonding (spun-bond, meltblown or carding), differential melt-point fiber bonding (bicomponent fibers put in through air dryer) or entangling (bydro-spun-lacing). The free fibers and capillary spaces allow structure to absorb some liquid which is part of what results in the high friction when contacting a wet floor.
  • Example 9 while being a thermally bonded non-woven has too much of its fibers tacked down from a tight embossed pattern. These leaves very few free-fibers and capillary spaces therefore resulting in a poor low glide when tested as an outer cuff.
  • the free fibers characteristic in these materials are also beneficial in providing attachment hooks for larger soils such as lint, hair and dust (capturing these soils is key function for cuffs).
  • the cuff can be formed by layering two different materials, it is also possible to form an effective cuff by choosing a material which has good characteristics as an outer cuff and on the inner side applying a scrim.
  • a material which has good characteristics as an outer cuff and on the inner side applying a scrim is shown by Example 12 where the scrim side was tested as an inner cuff and gave in a material to material wet glide of 2.447 N (0.55 lb.) of force while the opposite side was tested as an outer cuff and gave a material to surface wet glide of 2.891 N (065 lb) of force.
  • the opposite side typically has protrusions created during the forming or puncturing process and which makes it more textured and therefore result in a higher material to material friction (wet glide).
  • the material to surface glide for the textured part of the described apertured films is higher than the material to material friction (wet glide) for the female part of the film.
  • non-wovens such polypropylene, polyester, polyethylene, nylon, rayon etc. and/or natural fibers such as cellulose, hemp etc. could be applied as a complete coverage or partial coverage as zones to the outer part of the apertured film to form the cuff as a unitary layer.
  • the inner cuff characteristics and outer cuff characteristics need to be based on friction without presence of liquid (dry glide). Similar to wet mopping applications, for dry dusting the preferred characteristics are for the inner cuff side to have a materials to material friction dry (dry glide) that is lower than the material to surface friction dry (dry glide) for the outer cuff side.
  • the material to material friction or glide values should be less than about 2.669 N (0.6 lb.) force, preferably less than about 2.669 N (0.5 lb.) of force, and more preferably less than about 1.779 N (0.4 lb.) of force.
  • the material to surface friction or glide should be greater than about 1.779 N (0.4 lb.) force, preferably more than about 2.669 N (0.5 lb.) of force, and more preferably more than about 2.669 N (0.6 lb.) of force.
  • the ratio between inner cuff material to material friction or wet glide and outer cuff material to surface friction or glide should be less than about 1, preferably less than about 0.9, and more preferably less than about 0.75.
  • At least two layers of material are used to form the functional cuff. Those layers are partially attached to each other via selective attachment points between the inner cuff and outer cuff materials. Those selective attachment points allow for open spaces or channels between the layers. This not only provides spaces for soil which penetrates through the outer layer to get trapped, but provides the loop with more bulk which minimizes the cuffs propensity to flatten out and crease under the pressures the cuff goes through initially during manufacturing and then during mopping.
  • the functional cuffs can be in the form of a mono-layer or a multiple-layer laminate structure, and in the form of a loop or a non-loop structure.
  • the functional cuffs comprise a loop, as shown in Figures 2, 4a, and 4b of the drawings.
  • a looped functional cuff can be constructed by folding a strip of cuff material in half to form a loop and attaching it to the substrate.
  • Non-loop functional cuffs can also be used, particularly if the material used has sufficient rigidity.
  • the cleaning pads and sheets of the present invention can also comprise a combination of loop and/or non-loop, mono-layer and/or multiple-layer functional cuffs.
  • the functional cuffs can comprise an absorbent layer, as described below.
  • Functional cuffs can be formed as an integral part of the lower layer of a cleaning pad or the substrate of a cleaning sheet, or separately adhered to a cleaning pad and/or sheet. If the functional cuffs are an integral part of the lower layer of the cleaning pad and/or sheet, the functional cuffs are preferably a looped functional cuff formed by crimping the cleaning pad lower layer or cleaning sheet substrate, for example, in a Z-fold and/or C-fold.
  • the functional cuffs can be separately adhered to the lower layer of a cleaning pad and/or cleaning sheet via a variety of methods known in the art including, but not limited to, double-sided adhesive tape, heat bonding, gluing, ultrasonic welding, stitching, high-pressure mechanical welding, and the like.
  • Functional cuff(s) can be incorporated in traditional cleaning pads and sheets that are well-known in the art which comprise a variety of cellulosic and nonwoven material, such as sponges, foam, paper towels, polishing cloths, dusting cloths, cotton towels, and the like, both in a dry and pre-moistened form.
  • functional cuffs are particularly effective when incorporated in the cleaning pads of the present invention, as well as those described in copending U.S. Patent Application Serial No. 08/756,507 (Holt et al. ), copending U.S. Patent Application Serial No. 08/756,864 (Sherry et al. ), and copending U.S. Patent Application Serial No. 08/756,999 (Holt et al. ), all filed November 26, 1996; and copending U.S. Patent Application Serial No. 09/037,379 (Policicchio et al.), filed March 10, 1998 .
  • a cleaning sheet comprises one or more functional cuffs and a substrate, preferably a nonwoven substrate comprising a hydroentangled material, including, but not limited to, the substrates described in copending applications by Fereshtehkhou et al., U.S. Serial No. 09/082,349, filed May 20, 1998 (Case 6664M); Fereshtehkhou et al., U.S. Serial No. 09/082,396, filed May 20, 1998 (Case 6798M); and U.S. Patent No. 5,525,397, issued June 11, 1996 to Shizuno et al.
  • the substrate of the cleaning sheet has at least two regions, where the regions are distinguished by basis weight.
  • the substrate can have one or more high basis weight regions having a basis weight of from about 30 to about 120 g/m 2 , preferably from about 40 to about 100 g/m 2 , more preferably from about 50 to about 90 g/m 2 , and still more preferably from about 60 to about 80 g/m 2 , and one or more low basis weight regions, wherein the low basis weight region(s) have a basis weight that is not more than about 80%, preferably not more than about 60%, more preferably not more than about 40%, and still more preferably not more than about 20%, of the basis weight of the high basis weight region(s).
  • the substrate of the cleaning sheet will preferably have an aggregate basis weight of from about 20 to about 110 g/m 2 , more preferably from about 40 to about 100 g/m 2 , and still more preferably from about 60 to about 90 g/m 2 .
  • One or more functional enff(s) can be applied to, or formed as an integral part of, cleaning pads and sheets in a variety of locations on the pads and sheets.
  • the functional cuff(s) can be situated along the mid-line of the cleaning pad or sheet (in the x-y plane) along either the x-dimension or the y-dimension.
  • the cleaning pad or sheet comprises two functional cuffs situated at or near opposite edges (e.g., the leading and trailing edges of the pad and/or sheet, in terms of the y-dimension) of the cleaning pad or sheet.
  • the functional cuff(s) arc placed in a location such that their length is perpendicular to the back and forth mopping or wiping direction used by the consumer.
  • the present invention further encompasses articles of manufacture comprising the above-described cleaning pad and/or sheet comprising improved functional cuffs in association with a set of instructions, which can be combined with a package, carton, or other container.
  • the present invention also encompasses articles of manufacture comprising the above-described improved cleaning implement in association with a set of instructions, which can be combined with a package, carton, or other container.
  • the phrase "in association with” means the set of instructions are either directly printed on the cleaning sheet itself or presented in a separate manner including, but not limited to, a brochure, print advertisement, electronic advertisement, and/or verbal communication, so as to communicate the set of instructions to a consumer of the article of manufacture.
  • the set of instructions preferably comprise the instruction to use the cleaning pad and/or sheet comprising improved functional cuffs for hard surface cleaning with a cleaning implement, such as a floor mop, having a handle and a mop head.
  • the set of instructions can further comprise instructions to use the cleaning pad and/or sheet comprising improved functional cuffs or any other kind of cleaning pad with a floor mop having a stepped design mop head configured as previously described herein.
  • the instruction might instruct using the cleaning sheet with a floor mop having a stepped design mop head.
  • Other instructions might instruct a user to attach the cleaning sheet or pad to the mop head, move the floor mop, and then remove the cleaning sheet from the mop head.

Landscapes

  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Polarising Elements (AREA)
  • Cleaning In General (AREA)

Claims (10)

  1. Reinigungsvorrichtung (20) für die Reinigung harter Oberflächen, umfassend:
    (a) einen Griff (32);
    (b) einen Moppkopf (22), der drehbar an dem Griff (32) befestigt ist, wobei der Moppkopf (22) über ein Kissen (48) verfügt, das eine untere Oberfläche bildet;
    (c) mindestens ein erhobenes Element (148), das abnehmbar an der unteren Oberfläche des Kissens (48) befestigt ist, so dass der Moppkopf (22) in der Lage ist, sich relativ zur zu reinigenden Oberfläche zu drehen, wobei das erhobene Element (148) auf der unteren Oberfläche im Wesentlichen zentriert ist, und
    (d) ein absorbierendes Reinigungskissen (44), das an das erhobene Element (148) angekoppelt ist und abnehmbar am Moppkopf (22) befestigt werden kann
  2. Reinigungsvorrichtung (20) nach Anspruch 1, wobei die Breite des erhobenen Elements (148) geringer ist als die Breite des Moppkopfs (22).
  3. Reinigungsvorrichtung nach Anspruch 1, wobei die Länge des erhobenen Elements (148) geringer ist als die Länge des Moppkopfs (22).
  4. Reinigungsvorrichtung (20) nach Anspruch 1, wobei die Ränder des erhobenen Elements (148) entweder eckig, abgerundet, abgewinkelt, strukturiert, glatt oder jegliche Kombination davon sind.
  5. Reinigungsvorrichtung (20) nach Anspruch 1, wobei das erhobene Element (148) im Allgemeinen nicht komprimierbar ist
  6. Reinigungsvorrichtung (20) nach Anspruch 1, wobei das erhobene Element (148) im Allgemeinen komprimierbar ist.
  7. Reinigungsvorrichtung (20) nach Anspruch 1, wobei die Oberfläche des erhobenen Elements (148), die zur zu reinigenden Oberfläche zeigt, Unterbrechungen darin aufweist.
  8. Reinigungsvorrichtung (20) nach Anspruch 1, ferner ein zweites erhobenes Element umfassend, das am ersten erhobenen Element befestigt ist.
  9. Reinigungsvorrichtung (20) nach Anspruch 8, wobei die Breite des zweiten erhobenen Elements geringer ist als die Breite des ersten erhobenen Elements.
  10. Reinigungsvorrichtung (20) nach Anspruch 8, wobei die Dicke des zweiten erhobenen Elements geringer ist als die Dicke des ersten erhobenen Elements.
EP01995146A 2000-11-27 2001-11-20 Verbessertes Reinigungsgerät mit abnehmbarem Erhöhungselement Expired - Lifetime EP1345524B1 (de)

Applications Claiming Priority (3)

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US72302600A 2000-11-27 2000-11-27
US723026 2000-11-27
PCT/US2001/043358 WO2002041746A2 (en) 2000-11-27 2001-11-20 Cleaning implement for cleaning hard surfaces

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EP1345524A2 EP1345524A2 (de) 2003-09-24
EP1345524B1 true EP1345524B1 (de) 2007-10-17

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US7055204B2 (en) 2003-03-11 2006-06-06 The Evercare Company Cleaning device
US7591040B2 (en) 2003-12-18 2009-09-22 Kimberly-Clark Worldwide, Inc. Cleaning tool for removing larger and smaller sized particles
US7690069B2 (en) 2005-12-14 2010-04-06 Kimberly-Clark Worldwide, Inc. Cleaning tool with attachment projections providing additional cleaning functionalities
DE102012017971A1 (de) 2012-09-12 2014-03-13 Carl Freudenberg Kg Flachwischbezug mit zwei Reinigungsflächen
US10542862B2 (en) 2015-10-02 2020-01-28 The Procter & Gamble Company Cleaning pad having preferred performance with scrubbing strip
US10064534B2 (en) 2015-10-02 2018-09-04 The Procter & Gamble Company Cleaning pad having preferred construction
US20170095132A1 (en) 2015-10-02 2017-04-06 The Procter & Gamble Company Cleaning Pad Having Preferred Performance With Water
US10617274B2 (en) 2015-10-02 2020-04-14 The Procter & Gamble Company Cleaning pad having correlated cleaning performance
US10492656B2 (en) * 2015-10-02 2019-12-03 The Procter & Gamble Company Cleaning pad having preferred performance with representative cleaning solution

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JPH04114620A (ja) * 1990-09-01 1992-04-15 Hookii:Kk 拭き掃除具
CN2125362U (zh) * 1992-05-18 1992-12-23 杨建林 塑料海绵拖把
JP2981110B2 (ja) * 1993-03-01 1999-11-22 花王株式会社 清掃用具
CN2193713Y (zh) * 1994-04-12 1995-04-05 高秀彩 一种组装式拖把
US6101661A (en) * 1997-03-20 2000-08-15 The Procter & Gamble Company Cleaning implement comprising a removable cleaning pad having multiple cleaning surfaces
CN2312669Y (zh) * 1997-06-23 1999-04-07 许兴源 多向性拖把
EP2374397A3 (de) * 1998-11-09 2012-01-11 The Procter & Gamble Company Vorbefeuchtete Wischtücher, und Verfahren zur Verwendung
US20020050016A1 (en) * 2000-02-24 2002-05-02 Willman Kenneth William Cleaning sheets comprising a polymeric additive to improve particulate pick-up and minimize residue left on surfaces and cleaning implements for use with cleaning sheets
JPH11244210A (ja) * 1998-12-25 1999-09-14 Duskin Co Ltd 清掃具

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WO2002041746A2 (en) 2002-05-30
DE60131017D1 (de) 2007-11-29
CA2426042C (en) 2006-10-10
CN100508866C (zh) 2009-07-08
AU2002225657A1 (en) 2002-06-03
DE60131017T2 (de) 2008-07-31
CA2426042A1 (en) 2002-05-30
ES2295238T3 (es) 2008-04-16
CN1633254A (zh) 2005-06-29
MXPA03004621A (es) 2003-09-05
ATE375747T1 (de) 2007-11-15
JP2004513728A (ja) 2004-05-13
EP1345524A2 (de) 2003-09-24
WO2002041746A3 (en) 2002-10-10
CN101438950A (zh) 2009-05-27

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