WO2014205015A1

WO2014205015A1 - Laminate cleaning implement

Info

Publication number: WO2014205015A1
Application number: PCT/US2014/042822
Authority: WO
Inventors: Donald Carroll Roe; Jill Marlene Orr; John Joseph Curro
Original assignee: The Procter & Gamble Company
Priority date: 2013-06-18
Filing date: 2014-06-18
Publication date: 2014-12-24
Also published as: US20140366293A1; EP3010387A1; EP3010387B1; US9974424B2

Abstract

A laminate cleaning implement with a facing sheet, a substrate, and optionally a backing sheet. The facing sheet, the substrate, and the optional backing sheet are mechanically intermeshed. The mechanically intermeshing can provide one or more discrete tufts protruding outwardly from the laminate.

Description

LAMINATE CLEANING IMPLEMENT

FIELD OF THE INVENTION

The present invention is generally relates to a laminate cleaning implement, and more particularly to a multilayer laminate wherein at least one layer is a substrate.

BACKGROUND OF THE INVENTION

Many cleaning products, including shampoo, body wash, dentifrice, and hard surface cleaners, are sold containing water. The water in the formula adds to the weight of the products and translates into greater shipping and storage costs. Additionally, these types of products also have disadvantages in terms of packaging, storage, transportation, and convenience of use.

In order to use many cleaning products, the user must dispense the cleaning product from a bottle or other closed vessel onto the target surface, and then utilizing a sponge, towel, brush, or other implement distribute the product on the surface and, if desired, absorb any excess product, potentially with another implement or substrate.

This practice is widely used, but is often inefficient. For instance, when a caregiver washes a pet she must wet the pet, open the shampoo, put shampoo on the pet, rub the shampoo into the pet's coat, and then rinse the pet. This process must be repeated multiple times to clean the entire pet and it can be particularly difficult to adequately clean the legs, abdomen, and buttocks of the animal. Furthermore, if the caregiver is using a bottled shampoo, she must repeatedly handle the shampoo container with wet, slippery, soapy hands to dispense shampoo. All of this must be done while keeping the pet in the washing area. Since washing a pet can be difficult, the user may rush and not thoroughly clean the pet.

It would be desirable to have a cleaning product combined with an implement to make cleaning more efficient. However, making these combination products can be cumbersome. For instance, some products have a cleaning product sprayed onto an outer surface of an assembled cleaning implement and a drying step is required before the cleaning product can be packaged. Other combination products have a cleaning composition residing within a cleaning implement, however, processing steps, such as adding texture to a surface of the cleaning implement, must be completed before the cleaning composition is combined with the other parts of the cleaning implement.

It would also be desirable for such a cleaning product to capture the removed soil from the animate and/or inanimate surfaces being cleaned. Accordingly, there is a need for a laminate cleaning implement comprising a substrate that provides cleaning benefits, soil capture benefits, streamlines the cleaning process, and allows for a simplified manufacturing method. The cleaning implement can eliminate the need to carry and store cumbersome bottles, bars, jars, tubes, and other forms of clutter associated with cleaning products. Additionally, the cleaning implement can be designed to provide superior cleaning to the intended surface and soil removal from the intended surface. Furthermore, if the laminate cleaning implement is disposable it can be more sanitary than using a sponge, washcloth, or other cleaning implement intended for extensive reuse, because such implements can develop bacterial growth, unpleasant odors, and other undesirable characteristics related to repeated use.

SUMMARY OF THE INVENTION

A laminate cleaning implement comprising: (a) a facing sheet comprising a fibrous nonwoven; (b) a backing sheet; and (c) a substrate comprising an active agent wherein the substrate is disposed between the facing sheet and the backing sheet and wherein upon exposure to conditions of intended use the active agent is released; wherein the facing sheet, the substrate, and the backing sheet are mechanically intermeshed to provide one or more discrete tufts protruding outwardly from the laminate and wherein the tufts comprise a portion of the substrate.

A laminate cleaning implement comprising: (a) a facing sheet; (b) a backing sheet; and (c) a substrate comprising an active agent wherein the substrate is disposed between the facing sheet and the backing sheet wherein upon exposure to conditions of intended use the active agent is released; wherein the facing sheet, the substrate, and the backing sheet are mechanically intermeshed to provide one or more discrete tufts protruding outwardly from the laminate and wherein a portion of the substrate extends through the facing sheet at the tufts.

A laminate cleaning implement comprising: (a) a facing sheet; (b) a substrate comprising an active agent wherein upon exposure to conditions of intended use the active agent is released; and (c) optionally a backing sheet; wherein the facing sheet, the substrate, and optionally the backing sheet are mechanically intermeshed.

In still another example of the present invention, a laminate cleaning implement comprising (a) a facing sheet and (b) a substrate comprising an active agent wherein upon exposure to conditions of intended use the active agent is released, wherein the facing sheet and substrate are mechanically intermeshed, and optionally, wherein a composition, such as a composition comprising a soil capture agent, is present on the facing sheet, is provided. BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter of the present invention, it is believed that the invention can be more readily understood from the following description taken in connection with the accompanying drawings, in which:

FIG. 1 is a perspective view of a tufted laminate web suitable for use in a cleaning implement of the present invention;

FIG. 2 is an is an enlarged perspective view of a portion of the web shown in FIG. 1 ; FIG. 3 is a perspective view of a tufted laminate web suitable for use in a cleaning implement of the present invention;

FIG. 4 is an is an enlarged perspective view of a portion of the web shown in FIG. 3; FIG. 5 is a schematic representation of a top view of a portion of an indented web suitable for use in a cleaning implement of the present invention;

FIG. 6 is schematic representation of an enlarged cross-sectional view of section 6-6 of FIG. 5;

FIG. 7 is a perspective view of tufted and bonded laminate web suitable for use in a cleaning implement of the present invention;

FIG. 8 is an enlarged perspective view of a portion of the web shown in FIG. 9;

FIG. 9 is a top view of a tufted and bonded web suitable for use in a cleaning implement of the present invention;

FIG. 10 is an enlarged cross-sectional view of a portion of the web shown in FIG. 9; and

FIG. 11 is a perspective view of an apparatus for forming the web for use in the present invention. DETAILED DESCRIPTION OF THE INVENTION

The laminate cleaning implement can comprise a facing sheet, a backing sheet, and a substrate disposed between the facing sheet and the backing sheet that can be used to clean and/or capture soil from any surface, hard or soft. The substrate can comprise an active agent that can be used to clean any surface including hard surfaces (i.e., kitchen countertops, bath tubs, toilets, toilet bowls, sinks, floors, walls, teeth, cars, windows, mirrors, dishes), soft surfaces (i.e., fabric, hair including human hair and pet hair, skin, carpet, crops, plants), and combinations thereof. Soon after the cleaning implement is exposed to conditions of intended use, the substrate becomes dispersible and the active agent can be distributed across the surface to be cleaned or treated. At least a portion of the facing sheet, the backing sheet, and the substrate can be mechanically intermeshed to form a coherent laminate cleaning implement. The mechanical intermeshing can be any process that combines the sheets with the substrate without using adhesive, bonding, or sewing. Non-limiting examples of mechanical intermeshing can include nested embossing, male/female embossing, and SELFing (a process for making a Structural Elastic Like Film).

The mechanical intermeshing can create textured portions on at least a portion of the surface of the facing sheet and backing sheet, which can include protrusions, depressions, apertures, embossing, debossing, and combinations thereof. The textured portion can improve the cleaning functionality of the implement as well as increase the surface area of the laminate cleaning implement, which can increase the rate the substrate becomes dispersible after being in contact with conditions of intended use.

In one example, the textured portions can be made by SELFing, which creates protrusions that extend outwardly from the facial sheet, referred to herein as tufts, on one side of the laminate cleaning implement and depressions, referred to herein as indentations, on the opposite side of the laminate cleaning implement. In another example, the tufts can comprise a portion of the substrate. In another example, the facing sheet ruptures during SELFing such that portions of the substrate extend through the facing sheet at the tufts.

Intermeshing the facing sheet, the backing sheet, and the substrate can help simplify manufacturing as well as improve performance of the cleaning implement. In one example, the substrate can be a solid before it is exposed to conditions of intended use. Combining a solid substrate with the facing and backing sheets can simplify manufacturing by eliminating the drying step. It can also be easier to control the three-dimensional structure of the textured portions, especially when compared to spraying a liquid over the sheets, which can enhance both the appearance and cleaning effectiveness of the implement. Finally, the substrate can comprise enough cleaning composition to clean a large area, if desired. This allows the laminate cleaning implement to have a wide variety of uses including cleaning large pets, cars, hard surfaces, or humans, with only one cleaning implement.

In order to use the laminate cleaning implement, the user exposes the cleaning implement to conditions of intended use. As used herein, "conditions of intended use" means the temperature, physical, chemical, and/or mechanical conditions that a substrate is exposed to when it is used as a cleaning implement.

The facing sheet can have a textured portion on the surface. The textured portion can increase the effective available surface area and therefore when the laminate is exposed to conditions of intended use, such as water or another aqueous solution, the water or solution can more quickly penetrate through the facing sheet and come into contact with the substrate.

In one example, the substrate can include an active agent. As used herein, "active agent" or "active" means an additive that produces an intended effect in an environment external to a substrate, such as when the substrate is exposed to conditions of intended use. In one example, an active agent treats a surface, such as a hard surface and/or a soft surface. In another example, an active agent creates a chemical reaction (i.e., foaming, fizzing, coloring, warming, cooling, lathering, disinfecting). In yet another example, an active agent treats an environment (i.e., deodorizes, adsorbs odor, purifies, perfumes air). In yet another example, the active agent binds a target substance, such as soil.

Active agents may be any suitable additive that produces an intended effect under intended use conditions of the substrate. For example, the active agent may be selected from the group consisting of: personal cleansing and/or conditioning agents such as hair care agents including shampoo agents, skin cleansing agents, hair conditioning agents, hair coloring agents, bleaching agents, skin care agents, surfactants, moisturizers, protectants, barrier materials, smoothing agents, lubricants, fabric care agents, fabric softening agents, fabric care stain removal agents, soil release agents, soil-capture or binding agents, dispersing agents, dishwashing agents (for hand dishwashing and/or automatic dishwashing machine applications), hard surface cleansing agents, bleaching agents, carpet care agents, make-up removal agents, deposition aids, perfumes, odor absorbing agents, tooth care agents that can comprise abrasives for humans and pets, ear care agents for humans and pets, and mixtures thereof.

One or more classes of chemicals may be useful for one or more of the active agents. For example, surfactants may be used for any number of the active agents. Likewise, bleaching agents may be used for fabric care, hard surface cleaning, dishwashing and even teeth whitening. Therefore, one of ordinary skill in the art will appreciate that the active agents will be selected based upon the desired intended use of the cleaning implement made therefrom.

In another example, a second active agent can be deposited on or incorporated into the facing sheet and/or the backing sheet.

As used herein, the term "aperture", refers to a hole. The apertures can either be punched cleanly through the facing sheet, the backing sheet, and/or the substrate so that the material surrounding the aperture lies in the same plane as the facing sheet, backing sheet, or substrate prior to the formation of the aperture (a "two dimensional" aperture), or holes formed in which at least some of the material surrounding the opening is pushed out of the plane of the facing sheet, backing sheet, and/or substrate. In the latter case, the apertures may resemble a protrusion or depression with an aperture therein, and may be referred to herein as a "three dimensional" aperture, a subset of apertures. The apertures can be created by any suitable means including die cut holes, slitting and stretching the sheets and/or substrate, and combinations thereof. The laminate cleaning implement can comprise one or more sheets comprising apertures.

As used herein, the term "bicomponent fibers" refers to fibers which have been formed from at least two different polymers extruded from separate extruders but spun together to form one fiber. Bicomponent fibers are also sometimes referred to as conjugate fibers or multicomponent fibers. The polymers are arranged in substantially constantly positioned distinct zones across the cross-section of the bicomponent fibers and extend continuously along the length of the bicomponent fibers. The configuration of such a bicomponent fiber may be, for example, a sheath/core arrangement wherein one polymer is surrounded by another, or may be a side-by-side arrangement, a pie arrangement, or an "islands-in-the-sea" arrangement.

As used herein, the term "biconstituent fibers" refers to fibers which have been formed from at least two polymers extruded from the same extruder as a blend. Biconstituent fibers do not have the various polymer components arranged in relatively constantly positioned distinct zones across the cross-sectional area of the fiber and the various polymers are usually not continuous along the entire length of the fiber, instead usually forming fibrils which start and end at random. Biconstituent fibers are sometimes also referred to as multiconstituent fibers.

As used herein, "disposable" refers to an implement that is disposed or discarded after a limited number of usage events. In one example, the disposable implement is used five or fewer times, in another example three or fewer times, in another example two or fewer times, and in another example the disposable implement is used only one time.

As used herein, "g/use" refers to grams per use. This is the unit used for rate of consumption and the method for measuring and/or calculating it is described in the Consumption Rate Test herein.

As used herein, "glove" refers to a covering for the hand having separate sections for each finger.

As used herein, "indicia" provides information to a potential user or user of the systems, liquid medication (e.g. the active contained therein) and sachets. The indicia can comprise many forms and present the information in many ways and in many types of media. Non-limiting examples of types of indicia include alpha-numeric indicia, pictures, drawings, illustrations, photographs, computer-produced images, colors, sounds, textures, shapes, symbols, letters, numbers, and combinations thereof. As used herein, "mitt" refers to a covering for the hand that is partially or wholly unseparated and that may include space for the thumb in the main enclosure or may provide space for the thumb in a separate enclosure for the thumb or may not include a thumb enclosure at all. This term is also applicable to an implement that covers only one or more digits of a user, such as in the case of a "finger mitt".

While the terms "glove" and "mitt" have been defined with respect to the human hand, similar structures could be utilized to cover or enclose other elements of human anatomy, such as foot coverings, or other items for which coverings of a particular shape are preferred.

As used herein, "joined" refers to configurations in which a first element is directly secured to a second element. Joined also includes configurations in which the first element is indirectly secured to the second element.

As used herein, the term "meltblowing" refers to a process in which fibers are formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity, usually heated, gas (for example air) streams which attenuate the filaments of molten thermoplastic material to reduce their diameter, which may be to microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface, often while still tacky, to form a web of randomly dispersed meltblown fibers. Meltblown fibers are micro fibers which may be continuous or discontinuous and are generally smaller than 10 microns in average diameter.

As used herein, the term "monocomponent" fiber refers to a fiber formed from one or more extruders using only one polymer. This is not meant to exclude fibers formed from one polymer to which small amounts of additives have been added for coloration, antistatic properties, lubrication, hydrophilicity, etc. These additives, for example titanium dioxide for coloration, are generally present in an amount less than 5 weight percent and more typically 2 weight percent.

As used herein, the term "non-round fibers" describes fibers having a non-round cross- section, and includes "shaped fibers" and "capillary channel fibers." Such fibers can be solid or hollow, and they can be tri-lobal, delta-shaped, and are preferably fibers having capillary channels on their outer surfaces. The capillary channels can be of various cross-sectional shapes such as "U-shaped", "H-shaped", "C-shaped" and "V-shaped". One preferred capillary channel fiber is T-401, designated as 4DG fiber available from Fiber Innovation Technologies, Johnson City, Term. T-401 fiber is a polyethylene terephthalate (PET polyester). As used herein, the term "nonwoven web" refers to a web having a structure of individual fibers or threads which are interlaid, but not in a repeating pattern as in a woven or knitted fabric, which do not have randomly oriented fibers. Nonwoven web or fabrics can be formed from many known processes, such as, for example, air laying processes, meltblowing processes, spunbonding processes, hydroentangling processes, spunlacing processes, and bonded carded web processes. Also, multi-layer webs, such as spunbond-meltblown-spunbond webs and the like made by multiple beam spunbond processes, can be used. Fibers can be bicomponent, multicomponent, multiconstituent, and the like, as known in the art. The basis weight of nonwoven fabrics is usually expressed in grams per square meter (gsm). The basis weight of the laminate web is the combined basis weight of the constituent layers and any other added components. Fiber diameters are usually expressed in microns; fiber size can also be expressed in denier, which is a unit of weight per length of fiber. The basis weight of laminate webs suitable for use in the present invention can range from 5 to 500 g/m².

As used herein, "on-the-hand implement" refers to a covering for the hand or portion of the hand such as a finger, thumb, or palm.

As used herein, "pet" means dogs, cats, small mammals such as gerbils, hamsters, chinchillas, rats, rabbits, guinea pigs, and ferrets, and/or other domesticated animals.

As used herein, "permanently joined" refers to configurations in which a first element is secured to a second element such that the elements generally cannot be separated from one another without at least partially destroying one or both of the elements.

As used herein, the term "polymer" is used in its conventional meaning, and generally includes, but is not limited to, homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, etc., and blends and modifications thereof. In addition, unless otherwise specifically limited, the term "polymer" includes all possible geometric configurations of the material. The configurations include, but are not limited to, isotactic, atactic, syndiotactic, and random symmetries. In general, any of the known polymer types can be used, for example, polyolefinic polymers such as polypropylene or polyethylene can be used either as monocomponent fibers or bicomponent fibers. Other polymers such as PVA, PET polyesters, metallocene catalyst elastomers, nylon and blends thereof can be used. Any or all of the polymers can be cross-linked if desired.

As used herein, "releasably joined" refers to configurations in which a first element is secured to a second element, such that the first element and the second element can be separated with no or minimal damage to the first and second elements. As used herein, "SELF" or "SELFing", refer to Procter & Gamble technology in which SELF stands for Structural Elastic Like Film. While the process was originally developed for deforming polymer film to have beneficial structural characteristics, it has been found that the SELFing process can be used to produce beneficial structures in other materials, such as fibrous materials. Processes, apparatus, and patterns produced via SELF are illustrated and described in U.S. Pat. Nos. 5,518,801; 5,691,035; 5,723,087; 5,891,544; 5,916,663; 6,027,483; and, 7,527,615.

As used herein, "spunbond fibers" refers to small diameter fibers which are formed by extruding molten thermoplastic material as filaments from a plurality of fine, usually circular capillaries of a spinneret with the diameter of the extruded filaments then being rapidly reduced. Spunbond fibers are generally not tacky when they are deposited on a collecting surface. Spunbond fibers are generally continuous and have average diameters (from a sample of at least 10) larger than 7 microns, and more particularly, between about 10 and 40 microns.

As used herein, "tuft", refers to a particular type of protrusion that may be formed in a nonwoven web. Tufts typically have a tunnel-like configuration, and in some cases may be open at one or both of their ends.

As used herein, "water-soluble material" means a material that is miscible in water with sufficient time and/or agitation. In other words, a material that is capable of forming a stable (does not separate for greater than 5 minutes after forming the homogeneous solution) homogeneous solution with water at ambient conditions.

As used herein, "usage event" refers to one three minute cycle of the Consumption Rate Test described herein.

As used herein, "ambient conditions" means 73°F ± 4°F (about 23°C ± 2.2°C) and a relative humidity of 50% ± 10%.

As used herein, the articles "a" and "an" when used herein, for example, "an anionic surfactant" or "a fiber" is understood to mean one or more of the material that is claimed or described.

The laminate cleaning implement can comprise any number of sheets. In one example, the laminate cleaning implement can comprise a facing sheet, a backing sheet, and a substrate disposed between the facing sheet and the backing sheet. After the cleaning implement is exposed to conditions of intended use, at least a portion of the substrate becomes dispersible and the substrate and/or active agent can be distributed across the surface to be cleaned or treated.

The facing sheet, the backing sheet, and the substrate comprising an active agent can be mechanically intermeshed to form a coherent laminate cleaning implement. In one example, the sheets are not mechanically deformed until they are intermeshed with the substrate to form a coherent laminate. After exposure to conditions of intended use, the substrate can release the active agent and the active agent can be dispersed across the surface to be cleaned. In one example, the condition of intended use is exposure to water. In another example, after exposure to conditions of intended use the substrate becomes a liquid or otherwise dispersible.

The mechanical intermeshing can create textured portions on at least a portion of a surface of the facing sheet and the backing sheet. The textured portion can include protrusions, depressions, apertures, embossing, debossing, and combinations thereof.

The textured portions can also assist in cleaning. For instance, the textured portions can provide additional abrasion which can be helpful in removing dirt and stains, especially tightly adhered stains, from a surface. The textured portions can also be customized depending on the desired use for the cleaning implement.

In one example, the cleaning implement can be used to clean a pet's coat and the textured portions can help penetrate the coat, which helps to disperse the substrate and any active agents throughout the coat as well as remove debris including hair and massage the pet's skin. In one example, the cleaning implement is a mitt or glove and the textured portions are on the portion of the glove that covers the user's fingers.

The textured portions can be randomly arranged or arranged in a repetitive pattern of some form on either side of the laminate cleaning implement. In one example, the textured portions are evenly distributed on the entire surface of the laminate. In another example, the textured portions are only located on a certain part of the cleaning implement, for instance portion(s) that are involved in scrubbing and/or the portion(s) of the cleaning implement that comprises the substrate.

In one example, the textured portions can be made by SELFing. SELFing creates protrusions, referred to herein as tufts. In one example, the tufts can protrude outwardly from the facing sheet or backing sheet and can comprise a portion of the substrate. The tufts can comprise loops the loops can be complete loops and/or the loops can partially extend and then break to form loose ends.

In another example, the tufts can protrude outwardly from the facing sheet and the facing sheet ruptures such that portions of the substrate extend through the facing sheet at the tufts. Whether or not the facing sheet ruptures depends on the ability of the facing sheet to extend and permanently deform during the mechanical deformation process. The facing sheet can break to form a volcano-like structure, may partially extend and then break on one side of the loop to form a flap, or may break without much extension forming an aperture. In one example, the textured portion can comprise protrusions. The protrusions can be from about 1 mm to about 10 mm tall, in another example from about 2 mm to about 8 mm tall, in another example from about 3 mm to about 7 mm tall, and in another example about 4 mm to about 6 mm tall.

In another example, one sheet, for instance the backing sheet, is water impermeable. In another example, the laminate cleaning implement further comprises a water impermeable substrate. The water impermeable substrate and/or water impermeable sheet can prevent the user's hand from getting wet and/or coming into contact with the cleaning composition during use. In one example, the water impermeable substrate and/or water impermeable sheet is adapted to be held by the user during cleaning. In another example, the impermeable substrate or impermeable sheet can be used to distribute the cleaning composition across the surface to be cleaned.

In another example, the laminate cleaning implement further comprises a rigid backing layer that can provide additional stiffness to the cleaning implement, which can make it easier to use.

The facing sheet and backing sheet can be any suitable material and the material can be selected based on the surface to be cleaned. For instance, if the laminate cleaning implement is intended to be used to clean something delicate or sensitive, such as human skin, then a material that feels softer can be selected for the sheet. However, if the cleaning implement is intended to be used to clean a more robust surface, then a material that feels stiffer or rougher can be selected. The softness or stiffness of the sheets can be changed depending on the basis weight of the constituent material, the size of the denier fibers, and the strength or stiffness of the constituent material.

In certain examples, the sheets can be nonwovens (i.e. a natural or synthetic nonwovens including fibrous and nonfibrous nonwovens), wovens, films (e.g. a formed film), sponges (e.g. a natural or synthetic sponge), polymeric netted meshes (i.e. a "scrim"), batting, spunbond, spunlace, hydroentangled, carded, needlepunch, or any other suitable material. In one example, the sheets can be fibrous nonwovens. In another example, one or both sheets are water-stable but water permeable.

In one example, the backing sheet is the same as the facing sheet. In another example, the backing sheet is a different material than the facing sheet. For example, the backing sheet can be stiffer than the facing sheet thereby making the laminate cleaning implement more rigid. In another example, each side of the cleaning implement can be used for a different purpose. For instance, the first side comprising the facing sheet can be used for a first purpose, such as distributing a first active agent, such as a shampoo, soap, body wash, or dish cleaner, across the surface to be cleaned and the second side comprising the backing sheet can be used for a second purpose, such as drying the surface and/or spread a second active agent, such as a conditioner or drying agent, across the surface.

The substrate can be any composition that can comprise an active agent, can become dispersible upon conditions of intended use, and can be subjected to a mechanical deformation process. Non-limiting examples of substrates can include open cell foams, as described herein and in U.S. Pat. No. 8,268,764 and U.S. Pat. App. Nos. 12/361,634, 12/633,415, and 13/440,475, dissolvable filament substrates, as described herein and in U.S. Pat. App. Nos. 13/229,791, 13/229,818, and 13/229,845, compliant doughs, as described herein and in U.S. Pat. No. 6,491,928 and U.S. Pat. App. No. 13/438,918, films, fibers including nonwoven fibers, webs including nonwoven webs, closed cell foams, pastes, particles, flakes, powders, and combinations thereof. Alternatively, the substrate may comprise a composition deposited onto a web or other surface via an aqueous composition and subsequently dried to localize it on the web.

The laminate cleaning implement can have a rate of consumption. This is a measure of how much of the substrate is used during a usage event. If the consumption rate is too low, then cleaning can be difficult due to reduced access to the substrate and the active agents. However, if the consumption rate is too high, then the substrate and active agents can be released too quickly and the laminate cleaning composition can run out of substrate and/or active agent before the entire surface is cleaned. The consumption rate can vary based on the properties of the substrate and the sheets.

In one example, the laminate will have a consumption rate of about 3 g/use to about 30 g/use, in another example from about 6 g/use to about 25 g/use, and in another example from about 10 g/use to about 20 g/use as determined by the Consumption Rate Test described herein. In alternate examples, the laminate cleaning implement will have a consumption rate of about 0.5 g/use to about 15 g/use, in another example from about 1.5 g/use to about 10 g/use, and in another example from about 3.5 g/use to about 6.5 g/use as determined by the Consumption Rate Test described herein.

In one example, the laminate cleaning implement can further comprise an attachment means to attach or releasably attach the laminate cleaning implement to another article. Non- limiting examples of attachment means can include hook and loop fasteners such as Velcro®, buttons, fasteners, snaps, magnets, clips, adhesives, refastenable adhesives, and combinations thereof. The article can be a cleaning implement such as a broom, vacuum, sweeper, sponge, or toilet bowl cleaner. In one example, the attachment means is attached to or releasably attached to the backing sheet.

In another example, the laminate cleaning implement can be made into, affixed to, or releasably attached to, a glove, mitt, or other on-the-hand implement. In one example, the on- the -hand implement can be adapted so it is ambidextrous. In one example, the on- the hand implement comprises a water impermeable substrate or water impermeable sheet that is adapted to be in contact with the user's hand during use. The on-the-hand implement comprises a slip resistant substrate or slip resistant sheet, thereby preventing the on-the-hand implement from twisting or slipping during use. In one example the water impermeable substrate or water impermeable sheet is slip resistant.

In another example, the on-the-hand implement only covers the palm of the user's hand, and does not cover the user' s fingers or back of the user' s hand. This cleaning implement can be attached to the user' s hand by one or more suitable attachment means including but not limited to an elastic or Velcro® strap.

In another example, the on-the-hand implement can be a mitt or glove and can comprise a grasping means. The grasping means can be a loop, hook, or tab. The grasping means can be attached to any portion of the on-the-hand implement. In one example, the grasping means can be attached to an interior portion of the on-the-hand implement and in another example the grasping means can be attached to an exterior portion and in another example the grasping means is attached to an exterior portion near a user's wrist. In another example, the grasping means can be formed by bonding the facing sheet to the backing sheet to provide a full or partial pocket, loop or hook, for one or more fingers of the user. The grasping means can also be attached to the water impermeable sheet or substrate. The grasping means can help a user turn the cleaning implement inside out as she takes it off her hand.

In another example, the on-the-hand implement comprises an adjustment means which can be any suitable means for permitting the on-the-hand implement to snugly accommodate different hand sizes. Suitable adjustment means, include but are not limited to, include, hook and loop fasteners such as Velcro® and the like, elastic members, elastic strands, strings including draw strings, gussets, cinches, buttons, fasteners, tabs, tongue and grove fasteners such as Zip- Lock® type fasteners, resealable tape, belts, clips, adhesives, such as refastenable adhesives, and combinations thereof.

In another example, the laminate cleaning implement can comprise a usage indicator. In one example, the usage indicator lets the user know when the laminate cleaning implement runs out of the substrate. The usage indicator can be a separate feature or it can be part of the substrate, or it may be a part of a graphic. Other suitable usage indicators can include, but are not limited to, pH (e.g., at a specific pH or pH range a noticeable event occurs such as color change, noise generation or cessation and the like and combinations thereof), temperature (e.g., the implement may feel warm or cold for its intended use and then revert to ambient temperature, or change temperature form ambient after a period of time), time (e.g., the indicator may change size shape, color etc. after a time period since it was exposed to water air, oxygen, shear or other force and the like), and the like and combinations thereof. In one example, the usage indicator can be a color that is associated with the substrate and the color changes or dissipates as the cleaning implement is used.

The facing sheet and/or backing sheet can comprise indicia. The indicia can be in the form of logos, trademarks, geometric patterns, images of the surfaces that the implement is intended to clean, instructions on how to use the cleaning implement including the function or purpose of one or both sides of the implement, other indicia, or combinations thereof.

The cleaning implement can be disposable. In one example, the cleaning implement is intended to be used only once before it is disposed of and contains enough substrate and active agent for one use. In another example, the cleaning implement can be adapted for multiple uses.

The cleaning implement can be packaged in a secondary container. In one example, the cleaning implement does not have to be individually wrapped and multiple cleaning implements can be packaged together in one secondary package. The secondary package can be any suitable package. Non-limiting examples can include a box, bag, and plastic and/or cellophane packaging.

In another example, the cleaning implement does not comprise a substrate. In another example, a liquid cleaning solution can be sprayed or poured onto the cleaning implement. This can be useful for spot-cleaning and/or in-between cleaning and can be sold in combination with a laminate cleaning implement comprising a substrate as a cleaning system. In one example, the two cleaning implements are co-packaged and in another example the two products are placed adjacent to or near each other in the store. In one example, a cleaning implement comprising a substrate can be used to bathe a pet and can be used in combination with an in-between cleaning implement that is an on-the-hand implement that does not comprise a substrate. The in-between implement can be sprayed with a liquid cleaning composition prior to use. The in-between implement can be used to spot clean areas like a pet' s muzzle or paws or can be used to quickly refresh the entire pet. The in-between mitt can be used on a pet as needed, while the cleaning implement is intended to be used intermittently, for example once every two weeks. The following examples are intended for illustrative purposes only and are not intended to limit the invention. Furthermore, the examples can be combined and duplicated to make more complex laminate cleaning implements, in particular cleaning implements with more than one substrate.

FIG. 1 shows a tufted laminate web 1 suitable for use in a laminate cleaning implement of the present invention, hereinafter referred to simply as web 1. Web 1 can be made by SELFing, as described herein. Web 1 comprises three layers. The layers are referred to herein as generally planar, two-dimensional sheets, such as backing sheet 20 and facing sheet 21, and a generally planar, substrate 22. As disclosed below, the sheets and substrate of web 1 can be joined by interlocking mechanical engagement resulting from the formation of tufts 6.

Web 1 has a first side 3 and a second side 5, the term "sides" being used in the common usage of generally planar two-dimensional webs, such as paper and films that have two sides when in a generally flat condition. Facing sheet 21 has first surface 13. Web 1 has a machine direction (MD) and a cross machine direction (CD) as is commonly known in the art of web manufacture.

In one example, the first surface 3 can be defined by textured portions on the first surface 13 of facing sheet 21 and at least one, but preferably a plurality of, discrete tufts 6. Tufts 6 can increase the surface area of first surface 3, which can increase the rate at which water can penetrate first surface 3 and dissolve substrate 22. Furthermore, tufts 6 can provide abrasion which can improve cleaning. For instance, if tufted laminate web 1 is being used in a cleaning implement for cleaning human or dog hair, the tufts can penetrate the hair or fur and allow for better removal of gross contamination.

The number, spacing, and dimensions of tufts 6 can be varied to give varying texture to first surface 3 of web 1. For example, if tufts 6 are closely spaced the first surface 3 of web 1 can have a terry cloth-like feel. Alternatively, tufts 6 can be arranged in patterns such as lines or filled shapes to create portions of a laminate web having greater texture, softness, bulk, absorbency or visual design appeal. For example, when tufts 6 are arranged in a pattern of one or more lines, the tufts can have the appearance of stitching. Tufts 6 can also be arranged to form specific shapes, such as designs, words or logos. Likewise, the size dimensions, such as the height, length and width of individual tufts 6 can be varied.

Backing sheet 20 can be a fibrous woven or nonwoven web comprising fibers having sufficient elongation properties to have portions formed into tufts 6. As described more fully below, tufts are formed by urging fibers out-of-plane in the Z-direction at discrete, localized, portions of backing sheet 20. The urging out-of-plane can be due to fiber displacement, i.e., the fiber is able to move relative to other fibers and be "pulled," so to speak, out-of-plane. More often, however, for most nonwoven backing sheets 20, the urging out of-plane is due to the fibers of tufts 6 having been at least partially plastically stretched and permanently deformed to form tufts 6.

It can be appreciated that a suitable nonwoven facing sheet 21 can comprise fibers capable of experiencing sufficient plastic deformation and tensile elongation, or are capable of sufficient fiber mobility, such that looped fibers 8 are formed. However, it is recognized that a certain percentage of fibers urged out of the plane of first surface 13 will not form a loop, but instead will break and form loose ends. Such fibers are referred to herein as "loose" fibers or "loose fiber ends" as shown in FIG. 2. Loose fiber ends 18 are not necessarily undesirable and in some embodiments, most or all of the fibers of tufts 6 can be loose fiber ends 18. Loose fiber ends 18 can also be the result of forming tufts 6 from nonwoven webs consisting of, or containing, cut staple fibers. In such a case, some number of the staple fiber ends may protrude into the tuft 6, depending upon such things as the number of staple fibers in the web, the staple fiber cut length, and the height of the tufts.

A representative tuft 6 for the embodiment of web 1 shown in FIG. 1 is shown in a further enlarged view in FIG. 2. As shown, tuft 6 comprises a plurality of looped fibers 8 that are substantially aligned such that tuft 6 has a distinct linear orientation and a longitudinal axis L. In the example shown in FIGS. 1 and 2, longitudinal axis L is parallel to the MD. In one example, all the spaced apart tufts 6 have generally parallel longitudinal axes L. The number of tufts 6 per unit area of web 1, i.e., the area density of tuft 6, can be varied from about 1 tuft per unit area, e.g., square centimeter to as high as about 100 tufts per unit area. In one example, there can be at least about 10 tufts, or at least about 20 tufts per square centimeter, depending on the end use. The area density does not need to be uniform across the entire area of web 1, for instance, tufts 6 can be in certain regions of web 1, such as in regions having predetermined shapes, such as lines, stripes, bands, circles, and the like. In another example, the tufts can be located on a portion of the laminate web that is intended to be used for cleaning, such as a portion that is intended to go across the palm of a user' s hand.

In some examples, another characteristic of tufts 6 is their generally open structure characterized by open void area 10 defined interiorly of tuft 6, as shown in FIG. 2. The shape of void area 10 is opposite to the shape of the tooth which is used to form the tuft 6. By "void area" is not meant completely free of any fibers, but is meant as a general description of its general appearance. Therefore, it may be that in some tufts 6, a loose fiber or a plurality of loose fibers may be present in the void area 10. By "open" void area is meant that the two longitudinal ends of tuft 6 are generally open and free of fibers, such that tuft 6 forms something like a "tunnel" structure, as shown in FIG. 2.

FIG. 3 shows a tufted laminate web 30 suitable for use in a laminate cleaning implement of the present invention, hereinafter referred to simply as web 30. Web 30 can be made by SELFing, as described herein. Similar to web 1, in FIGS. 1 and 2, web 30 comprises a backing sheet 40, a facing sheet 41, and a substrate 42. As disclosed below, the sheets and substrate of web 30 can be joined by interlocking mechanical engagement resulting in the formation of tufts 36.

Web 30 has a similar structure and can be made out of the same constituent fibers as web 1, in FIGS. 1 and 2. However, a difference between the tufted laminate web 1 and tufted laminate web 30 are the tufts.

Backing sheet 40 and/or substrate 42 can have sufficient elongation properties to have portions formed into tufts 36. Tufts 36 are formed by urging fibers or portions out-of-plane in the Z-direction at discrete, localized, portions of backing sheet 40 and substrate 42. The urging out-of-plane can be due to fiber displacement in the backing sheet 40 and substrate 42, i.e., the fiber is able to move relative to other fibers and be "pulled," so to speak, out-of-plane. In another example, the urging out-of-plane is due to the fibers of tufts 36 having been at least partially plastically stretched and permanently deformed to form tufts 36.

Facing sheet 41 can be a material including a film or a non woven web having sufficiently less elongation properties relative to backing sheet 40 and/or substrate 42, such that upon experiencing the strain from the mechanical deformation process, facing sheet 41 will rupture, e.g., by tearing due to extensional failure, such that portions of substrate 42 can extend through, (i.e., "punch through" so to speak), facing sheet 41 to form tufts 36 on first surface 33 of web 30, as shown in FIGS. 3 and 4.

Web 30 can have openings 45 with a distinct linear orientation and a longitudinal axis, which is oriented parallel to the longitudinal axis L of its corresponding tuft 36, as shown in FIG. 4. Likewise, openings 45 will also have a transverse axis generally orthogonal to longitudinal axis in the MD-CD plane.

As shown in FIG. 4, tufts 36 extend through openings 45 in facing sheet 41. Openings 45 are formed by locally rupturing facing sheet 41 by the process described in detail below, or by urging fibers of facing sheet 41 out of plane. Rupture may involve a simple splitting open of facing sheet 41, such that opening 45 remains a simple two-dimensional aperture. However, for some materials, such as polymer films, portions of facing sheet 41 can be deflected or urged out- of-plane (i.e., the plane of facing sheet 41) to form flap-like structures, referred to herein as flap, or flaps, 47. The form and structure of flaps 47 is highly dependent upon the material properties of facing sheet 41. Flaps 47 can have the general structure of one or more flaps, as shown in FIGS. 3 and 4. In other embodiments, flap 47 can have a more volcano-like structure, as if the tuft 36 is erupting from the flap 47.

In one example flaps 47 do not contribute significantly to the material of tufts 36, and particularly do not contribute significantly to the tactile quality of tufts 36.

In another example, flaps 47 may extend out of plane significantly, even being as high, so to speak, as the tufts 36 themselves. In this embodiment flaps 47 can cause the tufts 36 to be more resilient and less susceptible to flattening due to compressive or bending forces. Tufts 36 can be, in a sense, "punched through" facing sheet 41 and can be "locked" in place by frictional engagement with openings 45. In some embodiments, for example, the lateral width of opening 45 (i.e., the dimension measured parallel to its transverse axis) can be less than the maximum width of the tooth that formed the opening (per the process described below). This indicates a certain amount of recovery at the opening that tends to constrain tuft 36 from pulling back out through opening 45. The frictional engagement of the tufts and openings provides for a laminate web structure having permanent tufting on one side that can be formed without adhesives or thermal bonding.

FIGS. 5-6 show a schematic representation of a portion of an indented laminate web 50 suitable for use in a laminate cleaning implement of the present invention, hereinafter referred to simply as web 50. Web 50 is similar to web 1 and web 30, in FIGS. 1-2 and FIGS. 3-4 respectively, however web 50 comprises only two layers, facing sheet 54 and substrate 55, which can be joined by interlocking mechanical engagement resulting in the formation of indentations 56. Indentations 56 increase the surface area of first surface 51. In one example, an active agent can be disposed in the indentation.

A laminate cleaning implement with both a facing sheet and a backing sheet can be desirable but is not required. In some examples, two sheets can help ensure that the substrate does not build up on the tooling during the manufacturing process. The backing sheet can extended into the tufts, which can provide additional stiffness and support for the tufts and the backing sheet can also provide additional strength to the cleaning laminate.

In other examples, having only one sheet, either a backing sheet or a facing sheet, mechanically intermeshed with the substrate is desirable. For instance, this web can be easily combined with other laminate webs to form a laminate cleaning implement.

Web 50 can be made by SELFing, described hereafter, which produces tufts on one side of the laminate web and indentations on the other. Web 50 is intended to be used with the indentations 56 contacting the surface to be cleaned. In the examples described in FIGS. 1-4, the webs are intended to be used with the tufts contacting the surface to be cleaned.

Additional information on laminate webs made by SELFing can be found in U.S. Pat. No. 7,670,665.

FIGS. 7-8 show a tufted and bonded laminate web 70 suitable for use in the laminate cleaning implement of the present invention, hereinafter referred to simply as web 70. Web 70 is similar to tufted laminate web 1 discussed herein, except that the distal ends 77 of tufts 76 are bonded. In one example, the distal ends 77 of tufts 76 can be thermally melt-bonded such that adjacent fibers are at least partially bonded to form distally-disposed melt-bonded portions 79. Web 70 comprises a tufted intermediate web 75. Tufted intermediate web 75 comprises backing sheet 71, facing sheet 72, and substrate 73 is disposed between first and facing sheets 71 and 72.

After tufted intermediate web 75 is formed, the distal ends 77 of tufts 76 can be heated to thermally join the thermally melt-bondable fibers such that adjacent fiber portions are joined to one another to form tufts 76 having distally-disposed melt-bonded portions 79. In one example, the thermally melt-bondable portions comprise polyethylene.

The distally-disposed melt-bonded portions 79 can be made by application of thermal energy and pressure to the distal ends 77 of tufts 76. The size and mass of the distally-disposed melt-bonded portions 79 can be modified by varying the amount of heat energy imparted to the distal ends 77 of tufts 76, the line speed of the apparatus for making tufts, and the method of heat application. The distally-disposed melt-bonded portions can bond the substrate and the backing layer, the facing layer and the substrate, and the facing layer, the substrate, and the backing layer.

In another example, distally-disposed melt-bonded portions 79 can be made by application of radiant heat. That is, in one example a bonding roll can be replaced or supplemented by a radiant heat source, such that radiant heat can be directed toward tufted intermediate web 75 at a sufficient distance and corresponding sufficient time to cause fiber portions in the distally-disposed portions of tufts 76 to soften or melt. Radiant heat can be applied by any of known radiant heaters. In another example, a heated flat iron, such as a handheld iron for ironing clothes, can be held adjacent the distal ends of tufts 76, such that melting is effected by the iron.

A benefit of processing the tufted intermediate web 75 as described above is that melting the distal ends of tufts 76 can increase the friction or abrasion when the cleaning implement is used.

Another benefit is that the web can be put under a certain amount of pressure without compressing or flattening the tufts 76. As such, a three-dimensional web can be produced and set, or "locked in" to shape, so to speak by providing for thermal bonding after forming. Moreover, the distally disposed bonded or melt-bonded portions 79 can aid in maintaining the tufted, lofty structure of tufts 76 when web 70 is subjected to compression or shearing forces. For example, web 70 processed as disclosed above to have tufts 76 comprising fibers integral with but extending from first surface 74 and having distally-disposed melt-bonded portions 79 can have improved shape retention after compression due to winding onto a supply roll and subsequently unwinding, as well as compression from the package when the cleaning implement is stored. It is believed that by bonding together adjacent fibers at distal ends 77 of tufts 76, the tufts experience less random collapse upon compression; that is, the entire structure of tufts 76 tends to move together, thereby permitting better shape retention upon a disordering event such as compression and/or shear forces associated with cleaning.

FIGS. 9-10 show tufted and bonded laminate web 80 suitable for use in the laminate cleaning implement of the present invention, hereinafter referred to simply as web 80. Web 80 is similar to web 70, except web 80 can have melt-bonded portions that are not, or not only, at distally-disposed portions of tufts. Web 80 comprises a tufted intermediate web 85. Tufted intermediate web 85 comprises backing sheet 81, facing sheet 82, and substrate 87 that is disposed between first and facing sheets 81 and 82. In one example, surface melt-bonded portion 83 could be made on second surface 78 between rows of tufts 86. In another example, surface melt-bonded material portions 83 can be generally straight, parallel stripes or bands of melt- bonded material.

In the surface melt-bonded portions 83, the substrate 87 can be "squeezed" or otherwise displaced out of the of the surface melt-bonded portion. Surface melt-bonded portions 83 can be made according to any suitable method, including the methods used in FIGS. 7-8.

As shown in FIG. 10, web 80 can have distal melt-bonded portions 89 on the distal ends of tufts 86 as well as stripes, bands or patterns of surface melt-bonded portion 83, which bonds facing sheet 82, substrate 87, and the backing sheet 81. Surface melt-bonded portions 83 may be substantially only surface bonded, or, depending upon the time, pressure, and temperature during manufacturing, can be substantially bonded throughout web 80.

There are many variations that can result based on the use of the web 80. The surface melt-bonded portion 83 can be in rows which may form a type of perforation for tearing or may mechanically weaken web 80. Alternatively, it may be desired to only have intermittent or staggered surface melt-bonded portion 83 in some webs 80. This may be desired where strength of the material is important. Note that this description is for processing with a heated roll and/or a high pressure roll. For examples using adhesive bonding, the same structure of bonded regions can be achieved, but it would not, of course, be "melt-bonded". In general, it is not necessary that a band or stripe of surface melt-bonding be disposed between every row of tufts 86 and the number and placement of lines of surface melt-bonding can be varied as desired. Additionally, the surface melt-bonding can be discontinuous strips or bands of material that can appear, for example, as dashes or dots in the MD orientation.

Additional information on webs with melt-bonded portions can be found in U.S. Pat. No. 7,682,686.

Component Materials for Facing Sheet and Backing Sheet

The laminate cleaning implement can comprise one or more sheets. The sheets can comprise any suitable material. Suitable materials can be resilient enough that they resist tearing or shredding during normal use. In another example, the sheet(s) can be incorporated into a cleaning implement that can be used to wash a human or pet and therefore the sheets can be made out of a material that limits irritation to a user's skin. In another example, the laminate cleaning implement can also be subjected to a mechanical deformation process, such as SELFing, and thus a suitable material can be capable of experiencing sufficient tensile elongation and plastic deformation, or are capable of sufficient fiber mobility, such that out-of-plane texture is formed.

The sheets can comprise any suitable material including polymer films, woven webs, or nonwoven webs. In one example, the facing sheet and/or the backing sheet can be a nonwoven web comprised of substantially randomly oriented fibers. By "substantially randomly oriented" is meant that, due to processing conditions of the sheet, there may be a higher amount of fibers oriented in the MD than the CD, or vice- versa.

Nonwovens can be made out of a plurality of fibers which can include, natural fibers, synthetic fibers, and combinations thereof. In another example, the nonwovens can comprise a high loft batting material. High loft batting material can help the substrate lather. High loft batting material has a low density, as compared to similar non-high loft nonwoven material, and comprises a random array of void spaces throughout its structure. In another example, the nonwovens can be an airlaid nonwoven material comprising a combination of natural fibers, staple length synthetic fibers and a latex binder. The nonwoven material can be about 20% to about 80% by weight wood pulp fibers, about 10% to about 60% by weight staple length polyester fibers, and about 10% to about 25% by weight binder. In one example, the high loft batting material is incorporated into a sheet that is adapted to be adjacent to the user's hand when the implement is in use. In another example the high loft batting material is incorporated into a layer that is adjacent to the substrate.

In another example, the sheets can comprise an elastomer. The elastomer can be elastic strands and/or an elastic film. Any suitable elastic film known in the art can be used. Suitable elastic films may comprise polypropylene, polyethylene, polyolefins, styrene-isoprene-styrene, styrene-butadiene-styrene, or combinations thereof. Suitable elastic strands can be made of a resilient elastic thermoplastic material. Additional information on elastomers can be found in U.S. Pat. No. 7,432,413 and U.S. Pat. App. No. 12/687,527.

In another example, the sheets can be biodegradable. For example, the implement or components thereof could be made from a biodegradable material, such as a polyesteramide.

Suitable natural fibers for constructing the nonwoven webs can include but are not limited to cellulosic fibers, such as wood pulp fibers, cotton, and rayon. Suitable synthetic fibers include fibers commonly used in textiles, including but not limited to polyester (e. g. polyethylene terephthalate) and polypropylene, polyethylene, polyether, and combinations thereof. Suitable fibers can be made of biopolymers made from non-petroleum sources such as bio-derived polyethylene (bio-PE), bio-derived polypropylene (bio-PP), bio-derived polyethylene terephthalate (bio-PET), and bio-derived poly(ethylene-2,5-furandicarboxylate) (bio-PEF). These materials can be partially or completely derived from at least one renewable resource where a renewable resource refers to a natural resource that can be replenished within a 100 year time frame. Renewable resources include plants, animals, fish, bacteria, fungi, and forestry products and may be naturally occurring, hybrids, or genetically engineered organisms. Natural resources such as crude oil, coal, and peat which take longer than 100 years to form are not considered to be renewable resources. Other polymers derived from non-petroleum sources include starch-based polymers and cellulosics. Additionally, recycled resins such as post- consumer regrind r-HDPE, r-LLDPE, r-LDPE, r-PET, r-PEF, or r-PP can be used at 100% or blended with various resins. Polymers derived from renewable resources and recycled resins could be used on their own, or blended into petroleum-based polymers at varying levels in order to control the cost. Sources and methods of making polymers from non-petroleum sources can be found in U.S. App. No. 2011/0319849.

Various methods can be used to form the facing sheet and the backing sheet for use in the present invention. For instance, if the sheets are nonwoven webs they can be made by nonwoven dry forming techniques, such as air-laying, or alternatively by wet laying, such as on a papermaking machine, of a continuous web out of which the nonwoven webs are made. Other nonwoven manufacturing techniques, including but not limited to techniques such as spunbonding, meltblowing, carding, needle punching, hydroentangling, thermal bonding, through-air bonding, lamination methods may also be used, and combinations thereof.

The sheets can be subjected to various treatments, such as, but not limited to, physical treatment, such aperturing, embossing, ring rolling SELFing and the like; chemical treatment, such as, rendering part or all of the sheet hydrophobic, and/ or hydrophilic, and the like; thermal treatment, such as softening of fibers by heating, thermal bonding and the like; and combinations thereof.

Additional information on materials which are suitable for use as the sheets of the present invention can be found in the following patents: U.S. Pat. No. 3,862,472; U.S. Pat. No. 3,982,302; U.S. Pat. No. 4,004,323; U.S. Pat. No. 4,057,669; U.S. Pat. No. 4,097,965; U.S. Pat. No. 4,176,427; 4,130,915; U.S. Pat. No. 4,135,024; U.S. Pat. No. 4,207,367; U.S. Pat. No. 4,296,161; U.S. Pat. No. 4,682,942; U.S. Pat. No. 4,637,859; U.S. Pat. No. 5,223,096; U.S. Pat. No. 5,240,562; 5,556,509; and U.S. Pat. No. 5,580,423.

Substrates

After exposure to conditions of intended use, the substrate comprising an active agent can release the active agent and it can be spread across the area to be treated using the cleaning implement. The substrate can be lathering or non-lathering after exposure to conditions of intended use.

The substrate can releasably comprise an active agent. The active agent can be on the substrate or in the substrate and can be released when it the cleaning implement comes into contact with conditions of intended use, such as water.

Non-limiting examples of substrates can include open cell foams, dissolvable filament substrates, compliant doughs, films, fibers including nonwoven fibers, webs, powders, closed cell foams, pastes, substantially dry solids, particles, flakes, and combinations thereof. In another example, the substrate can be a semi-solid or liquid substrate.

The substrate can be disposed between the facing sheet and the backing sheet. The substrate can be disposed on substantially the entire cleaning implement or a portion of the cleaning implement. In one example, the substrate can be a flat, flexible substrate in the form of a pad, a strip, sheet or tape. In another example, the substrate is not completely plastically deformable and it may be broken, cracked, or fractured and held into place via the structure of the laminate cleaning implement.

The substrate may comprise a coating deposited onto a web via an aqueous solution an subsequently dried (i.e., water removed) to form at least a partial film on elements of the web. The substrate can be mostly dry, even dry to the touch, prior to being exposed to conditions of intended use. In one example, the substrate comprises less than or equal to about 10% moisture, such as water, by weight of substrate, in another example less than or equal to about 7%, in another example less than or equal to about 5%, and in another example less than or equal to about 3%, as determined by the Water Content Test Method described herein.

The substrate can quickly dissolve after it is exposed to conditions of intended use. In one example, the substrate can dissolve in less than about 60 seconds/gram (s/g), in another example less than about 30 s/g, in another example less than 20 s/g, in another example less than about 15 s/g, in another example less than about 10 s/g, in another example less than about 7 s/g, as determined by the Dissolution Test Method described herein.

The substrate can comprise an active agent which can be a surfactant, a polymer, and/or a plasticizer. When the cleaning implement is intended to be used on the skin, mucous membranes, scalp, or hair of a human or pet, all components of the substrate can be physiologically acceptable, i.e., they can be compatible with the skin, mucous membranes, the hair and/or the scalp.

The substrate can comprise a surfactant. In one example, the substrate is a lathering substrate and the surfactant can be a foaming agent.

Non-limiting examples of suitable surfactants can include anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof. For a substrate designed for use as soap, detergent, or shampoo the total level of surfactants should be sufficient to provide cleaning including stain, oil, dirt, and/or odor removal, and generally ranges from about 0.5% to about 95%. Further, surfactant systems comprising two or more surfactants that are designed for use in substrates may include all- anionic surfactant systems, mixed-type surfactant systems comprising anionic-nonionic surfactant mixtures, or nonionic-cationic surfactant mixtures or low- foaming nonionic surfactants.

Non limiting examples of anionic surfactants are described in U.S. Pat. Nos. 2,486,921, 2,486,922, and 2,396,278. Non limiting examples of anionic surfactants can be selected from the group consisting of alkyl and alkyl ether sulfates, sulfated monoglycerides, sulfonated olefins, alkyl aryl sulfonates, primary or secondary alkane sulfonates, alkyl sulfosuccinates, acid taurates, acid isethionates, alkyl glycerylether sulfonate, sulfonated methyl esters, sulfonated fatty acids, alkyl phosphates, acyl glutamates, acyl sarcosinates, alkyl lactylates, anionic fluorosurfactants, sodium lauroyl glutamate, and combinations thereof. Non limiting examples of suitable zwitterionic surfactants are described in U.S. Pat. Nos. 5,104, 646 and 5,106,609.

Non-limiting examples of suitable cationic surfactants are described in U.S. Pat. Nos. 4,228,042, 4,239,660, 4,260,529, 6,022,844, 6,004,922, 6,136,769, and 6,221,825.

Non-limiting examples of suitable nonionic surfactants include alkoxylated alcohols

(AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), Cio-Cis glycerol ethers, and the like. Additional suitable nonionic surfactants can be found in U.S. Pat. Nos. 4,133,779, 4,483,779, 4,681,704, 4,483,780, 4,565,647, and 6,482,994.

Additional suitable surfactants include those disclosed in U.S. Pat. No. 8,309,505 and those surfactants disclosed in McCutcheon' s Detergents and Emulsifiers, North American Edition (1986), Allured Publishing Corp.; McCutcheon' s, Functional Materials, North American Edition (1992), Allured Publishing Corp.

In another example, the substrate can comprise a polymer. Non-limiting examples of polymers can include synthetic polymers as described in U.S. Pat. No. 8,349,787 including polymers derived from acrylic monomers such as the ethylenically unsaturated carboxylic monomers and ethylenically unsaturated monomers as described in U.S. Pat. No. 5,582,786. The polymers which are suitable may also be selected from naturally sourced polymers including those of plant origin examples which are described in U.S. App. No. 61/ 120,786. Modified natural polymers are also useful as water-soluble polymer(s) in the present invention and are included in U.S. Pat. No. 8,349,787.

In one example, polymers can include polyvinyl alcohols, polyacrylates, polymethacrylates, copolymers of acrylic acid and methyl acrylate, polyvinylpyrrolidones, polyalkylene oxides, starch and starch derivatives, pullulan, gelatin, hydroxypropylmethylcelluloses, methycelluloses, carboxymethycelluloses, and combinations thereof. Suitable polyvinyl alcohols can include those available from Celanese Corporation (Dallas, Texas) under the CELVOL® trade name. Suitable hydroxypropylmethylcelluloses include those available from the Dow Chemical Company (Midland, Michigan) under the METHOCEL® trade name.

In another example, the polymer can comprise a polysaccharide, such as starch and/or a starch derivative, such as an ethoxylated starch and/or acid-thinned starch. Typical sources for starch-based materials can include cereals, tubers, roots, legumes and fruits. Native sources can include com, pea, potato, banana, barley, wheat, rice, sago, amaranth, tapioca, arrowroot, canna, sorghum, and waxy or high amylase varieties thereof. In another example, the substrate can comprise a plasticizer. Non-limiting examples of plasticizers can include polyols, copolyols, polycarboxylic acids, polyesters and dimethicone copolyols. Examples of useful polyols include, but are not limited to, glycerin, diglycerin, propylene glycol, ethylene glycol, butylene glycol, pentylene glycol, cyclohexane dimethanol, hexane diol, polyethylene glycol (200-600), sugar alcohols such as sorbitol, manitol, lactitol and other mono- and polyhydric low molecular weight alcohols (e.g., C2-C8 alcohols); mono di- and oligo-saccharides such as fructose, glucose, sucrose, maltose, lactose, and high fructose corn syrup solids and ascorbic acid.

In one example, the plasticizer can include glycerin and/or propylene glycol and/or glycerol derivatives such as propoxylated glycerol. In still another example, the plasticizer can be selected from the group consisting of glycerin, ethylene glycol, polyethylene glycol, propylene glycol, glycidol, urea, sorbitol, xylitol, maltitol, sugars, ethylene bisformamide, amino acids, and mixtures thereof

In another example, the substrate can comprise one or more colors and/or dyes that are incorporated into the substrate or are on the substrate. In one example, the colors and/or dyes can provide a visual signal when the substrate has been exposed to conditions of intended use and/or when an active agent is released from the substrate.

In one example, the substrate can be an open cell foam. The open cell foam can have a high degree of cell inter-connectivity. While not wishing to be bound by theory, it is believed that due to the high degree of cell inter-connectivity, the open cell foam can dissolve faster than a closed cell foam. The open cell foam can have a minimum level of interconnectivity between the cells, which is quantified by the Percent Open Cell Content.

The open cell foam can have a Percent Open Cell Content of from about 80% to about 100%, in one example from about 85% to about 97.5%, and in another example from about 90% to about 95%. The Percent Open Cell Content can be determined using the Gas Pycnometry Method described herein.

The open cell foam can have a minimum specific surface area. The open cell foam can have a specific surface area of from about 0.03 m²/g to about 0.25 m²/g, in one example from about 0.035 m²/g to about 0.22 m²/g, in another example from about 0.04 m²/g to about 0.19 m²/g, and in still another example from about 0.045 m²/ g to about 0.16 m²/g. The specific surface area can be determined using the Specific Surface Area Method described herein.

In one example, the open cell foam can be a lathering foam and can comprise a surfactant and the surfactant can be present from about 10% to about 75%, in another example from about 30% to about 70%, and in another example from about 40% to about 65% by weight of the substrate. In another example, the open cell foam dissolvable solid substrate is a non-lathering open cell foam and can comprise from about 10% to about 75%, in another example from about 15% to about 60%, and in another example from about 20% to about 50% by weight of the foam; wherein the surfactant comprises one or more of the surfactants described herein.

In one example, the open cell foam can comprise a polymer and the polymer may be present from about 10% to about 50% by weight of the foam, in one example from about 15% to about 40% by weight of the foam, and in yet another example from about 20% to about 30% by weight of the foam.

The open cell foam can comprise a plasticizer. In one example, the plasticizers can be present from about 1% to about 30% by weight of the foam; in another example from about 3% to about 25%; in another example from about 5% to about 20%, and in yet another example, from about 8% to about 15%.

Open celled foams as described herein can be made using the following method: (1) Preparing a processing mixture comprising surfactant(s), a polymer, and plasticizer; (2) Aerating the processing mixture by introducing a gas into the processing mixture to form an aerated wet mixture; (3) Forming the aerated wet mixture into one or more desired shapes; and (4) Drying the aerated wet mixture to form a porous dissolvable solid substrate.

The processing mixture is generally prepared by dissolving a polymer in the presence of water, a plasticizer, and a surfactant by heating followed by cooling. Then, the processing mixture is aerated, which can be accomplished by any means that introduces a gas into the mixture to form the aerated wet processing mixture. In one example, a continuous pressurized aerator (available from Morton Machine Co., Motherwell, Scotland) that is conventionally utilized within the foods industry can be used.

Then, the wet aerated processing mixture can be formed into the desired shape or shapes. One way to do this is to deposit the wet aerated mixture into one or more molds. Finally, the wet aerated processing mixture is dried. One way to dry the wet aerated mixture is to place it in a heated drying room with a temperature between 100° C and 150° C. After the mixture is dried, an open cell foam is created and can be removed from the molds if necessary.

Additional information on making open cell foams is disclosed in U.S. Pat. App. No. 13/561,298.

In one example, the substrate can be a dissolvable filament substrate. The dissolvable filament substrate can comprise filaments and/or fibers that can be interlaid and can be randomly oriented. In one example, the dissolvable filament substrate comprises filaments. As used herein, "filament" means an elongate particulate having a length greatly exceeding its diameter, i.e. a length to diameter ratio of at least about 10.

The filaments of can be spun from filament-forming compositions via suitable spinning processes operations, such as meltblowing and/or spunbonding.

The filaments can be monocomponent, bicomponent and/or multicomponent.

Filaments are typically considered continuous or substantially continuous in nature. Filaments are relatively longer than fibers (which are less than 5.08 cm in length).

In one example, one or more fibers may be formed from a filament as described herein, such as when the filaments are cut to shorter lengths (such as less than 5.08 cm in length). Thus, in one example, the fiber made from a filament as described herein, such as a fiber comprising one or more filament-forming materials. Therefore, references to filament and/or filaments also include fibers made from such filament and/or filaments unless otherwise noted. Fibers are typically considered discontinuous in nature relative to filaments, which are considered continuous in nature.

As used herein, "filament-forming material" means a material, such as a polymer or monomers capable of producing a polymer that can exhibit properties suitable for making a filament.

The filament-forming material can be any suitable material, such as a polymer or monomers capable of producing a polymer that exhibits properties suitable for making a filament, such as by a spinning process.

In one example, the filament comprises about 100% and/or greater than about 95% and/or greater than about 90% and/or greater than about 85% and/or greater than about 75% and/or greater than about 50% by weight on a dry filament basis and/or dry dissolvable filament substrate basis of one or more filament-forming materials. For example, the filament-forming material can comprise a polymer and in one example the polymer is a polyvinyl alcohol and/or starch.

As used herein, "by weight on a dry filament basis and/or dry dissolvable filament substrate basis" means that the weight of the filament and/or dissolvable filament substrate measured immediately after the filament and/or dissolvable filament substrate has been conditioned in a conditioned room at a temperature of 73°F ± 4°F (about 23°C ± 2.2°C) and a relative humidity of 50% ± 10% for 2 hours. In one example, "by weight on a dry filament basis and/or dry dissolvable filament substrate basis" means that the filament and/or dissolvable filament substrate comprises less than 20% and/or less than 15% and/or less than 10% and/or less than 7% and/or less than 5% and/or less than 3% and/or to 0% and/or to greater than 0% based on the weight of the filament and/or dissolvable filament substrate of moisture, such as water, for example free water, as measured according to the Water Content Test Method described herein.

In another example, the filament comprises one or more filament-forming materials and one or more active agents wherein the total level of filament-forming materials present in the filament is from about 5% to less than about 80% by weight on a dry filament basis and/or dry dissolvable filament substrate basis and the total level of active agents present in the filament is greater than about 20% to about 95% by weight on a dry filament basis and/or dry dissolvable filament substrate basis.

In another example, the filament-forming materials and active agents are present in the filament at a weight ratio of total level of filament-forming materials to active agents of about 4.0 or less and/or about 3.5 or less and/or about 3.0 or less and/or about 2.5 or less and/or about 2.0 or less and/or about 1.85 or less and/or less than about 1.7 and/or less than about 1.6 and/or less than about 1.5 and/or less than about 1.3 and/or less than about 1.2 and/or less than about 1 and/or less than about 0.7 and/or less than about 0.5 and/or less than about 0.4 and/or less than about 0.3 and/or greater than about 0.1 and/or greater than about 0.15 and/or greater than about 0.2.

In still another example, the filament comprises from about 10% and/or from about 15% to less than about 80% by weight on a dry filament basis and/or dry dissolvable filament substrate basis of a filament-forming material, such as polyvinyl alcohol polymer and/or a starch polymer, and greater than about 20% to about 90% and/or to about 85% by weight on a dry filament basis and/or dry dissolvable filament substrate basis of an active agent.

As used herein, "filament-forming composition" means a composition that is suitable for making a filament such as by meltblowing and/or spunbonding. The filament-forming composition comprises one or more filament-forming materials that exhibit properties that make them suitable for spinning into a filament. In one example, the filament-forming composition can comprise a polymer. In one example, the filament-forming composition may comprise one or more active agents. In another example, the filament-forming composition can comprise a polar solvent, such as water, into which some or all, of the filament-forming materials and/or the active agents are dissolved and/or dispersed. In another example, the filament-forming composition can comprise a plasticizer.

In another example, the filament and/or the filament-forming composition can comprise a crosslinking agent suitable for crosslinking one or more of the filament- forming materials present in the filaments of the present invention. In one example, the crosslinking agent comprises a crosslinking agent capable of crosslinking hydroxyl polymers together, for example via the hydroxyl polymers hydroxyl moieties. Non-limiting examples of suitable cros slinking agents include imidazolidinones, polycarboxylic acids and mixtures thereof. In one example, the crosslinking agent comprises a urea glyoxal adduct crosslinking agent, for example a dihydroxyimidazolidinone, such as dihydroxyethylene urea ("DHEU").

In one example the filament does not contain cellulose. As used herein, "non-cellulose- containing" means that less than about 5% and/or less than about 3% and/or less than about 1% and/or less than about 0.1% and/or about 0% by weight of cellulose polymer, cellulose derivative polymer and/or cellulose polymer is present in filament.

The dissolvable filament substrates can be made by any suitable method, including the methods in U.S. Pat. No. 7,291,300 and U.S. Pat. App. No. 13/229,818.

In addition, a plurality of the filaments can be collected and pressed into a film, thus resulting in a dissolvable film substrate comprising the one or more filament-forming materials and the one or more active agents that are releasable from the dissolvable film, such as when the film is exposed to conditions of intended use.

Laminate Cleaning Implement

One or more of the facing sheet, backing sheet, and the substrate may further comprise a soil capture agent that facilitates removal of soils from the surfaces being cleaned. "Soil" refers to organic or inorganic material, often particulate in nature that may include dirt, clays, food particulates, sebum or greasy residue, soot, etc. The soil capture agent may remain with the laminate cleaning implement such that soil removed from a surface becomes captured in and/or bound and/or adhered to and/or entrapped in the laminate cleaning implement.

A soil capture agent as described herein provides enhanced benefits in capturing soil. Such soil capture agents can be used singularly or in combination with other components to form a cleaning composition (e.g., liquid cleansing solution). In certain embodiments, such soil capture agents can include polymers. Such polymers can include several monomeric units thus it can be referred to as a copolymer rather than a homopolymer, which consists of a single type of monomeric unit. The polymers of the present disclosure may be a terpolymer (3 different monomeric units). The polymers of the present disclosure may be a random copolymer. In one example, a polymer of the present disclosure may be water-soluble and/or water-dispersible, which means that the polymer does not, over at least a certain pH and concentration range, form a two-phase composition in water at 23°C + 2.2°C and a relative humidity of 50% ± 10%.

In one example, the polymers of the present invention exhibit a Number Average Molecular Weight of less than 2,000,000 g/mol and/or less than 1,750,000 g/mol and/or less than 1,700,000 g/mol and/or less than 1,500,000 g/mol and/or greater than 500,000 g/mol and/or greater than 900,000 g/mol. In another example, the polymers exhibit a Number Average Molecular Weight of from about 500,000 to 2,000,000 g/mol and/or from about 900,000 to 1,700,000 g/mol and/or from about 1,000,000 to 1,500,000 g/mol.

In yet another example, the polymers of the present invention exhibit a charge density (at pH 4.5) of from about -0.1 meq/g and/or from about -0.05 meq/g and/or from about -0.02 meq/g and/or from about 0 meq/g and/or to about +0.1 meq/g and/or to about +0.09 meq/g and/or to about +0.08 meq/g and/or to about +0.06 meq/g and/or to about +0.05 meq/g and/or to about +0.02 meq/g as measured according to the Charge Density Test Method described herein. In still another example, the polymers of the present invention exhibit a charge density of from about - 0.1 meq/g to about +0.1 meq/g and/or from -0.05 meq/g to about +0.1 meq/g and/or from about 0 to less than +0.1 meq/g and/or to less than +0.09 meq/g and/or to less than +0.08 meq/g and/or to less than +0.06 meq/g and/or to less than +0.05 meq/g as measured according to the Charge Density Test Method described herein. In one example, the polymers of the present invention exhibit an excess charge (charge density) of from about 0 to about 0.1 meq/g. In another example, the polymers of the present invention exhibit an excess charge (charge density) of about 0.05 meq/g or less.

In another example, the polymers exhibit a Polydispersity Index of less than 2.5 and/or of less than 2.0 and/or less than 1.7 and/or less than 1.5 and/or less than 1.3.

In one example, a polymer of the present invention comprises two or more monomeric units selected from the group consisting of: a. nonionic monomeric units; b. anionic monomeric units; c. cationic monomeric units; d. zwitterionic monomeric units; and e. mixtures thereof.

a. Nonionic Monomeric Units

The nonionic monomeric units may be selected from the group consisting of: nonionic hydrophilic monomeric units, nonionic hydrophobic monomeric units, and mixtures thereof.

Non-limiting examples of nonionic hydrophilic monomeric units suitable for the present invention include nonionic hydrophilic monomeric units derived from nonionic hydrophilic monomers selected from the group consisting of: hydroxyalkyl esters of α,β-ethylenically unsaturated acids, such as hydroxyethyl or hydroxypropyl acrylates and methacrylates, glyceryl monomethacrylate, α,β-ethylenically unsaturated amides such as acrylamide, N,N- dimethylmethacrylamide, N-methylolacrylamide, α,β-ethylenically unsaturated monomers bearing a water-soluble polyoxyalkylene segment of the poly(ethylene oxide) type, such as poly(ethylene oxide) a-methacrylates (Bisomer S20W, S10W, etc., from Laporte) or α,ω- dimethacrylates, Sipomer BEM from Rhodia (ω-behenyl polyoxyethylene methacrylate), Sipomer SEM-25 from Rhodia (ω-tristyrylphenyl polyoxyethylene methacrylate), α,β- ethylenically unsaturated monomers which are precursors of hydrophilic units or segments, such as vinyl acetate, which, once polymerized, can be hydrolyzed in order to give rise to vinyl alcohol units or polyvinyl alcohol segments, vinylpyrrolidones, α,β-ethylenically unsaturated monomers of the ureido type, and in particular 2-imidazolidinone-ethyl methacrylamide (Sipomer WAM II from Rhodia), and mixtures thereof. In one example, the nonionic hydrophilic monomeric unit is derived from acrylamide.

Non-limiting examples of nonionic hydrophobic monomeric units suitable for the present invention include nonionic hydrophobic monomeric units derived from nonionic hydrophobic monomers selected from the group consisting of: vinylaromatic monomers such as styrene, alpha-methylstyrene, vinyltoluene, vinyl halides or vinylidene halides, such as vinyl chloride, vinylidene chloride, C1-C12 alkylesters of α,β-monoethylenically unsaturated acids such as methyl, ethyl or butyl acrylates and methacrylates, 2-ethylhexyl acrylate, vinyl esters or allyl esters of saturated carboxylic acids, such as vinyl or allyl acetates, propionates, versatates, stearates, α,β-monoethylenically unsaturated nitriles containing from 3 to 12 carbon atoms, such as acrylonitrile, methacrylonitrile, a-olefins such as ethylene, conjugated dienes, such as butadiene, isoprene, chloroprene, and mixtures thereof.

b. Anionic Monomeric Units

Non-limiting examples of anionic monomeric units suitable for the present invention include anionic monomeric units derived from anionic monomers selected from the group consisting of: monomers having at least one carboxylic function, for instance α,β-ethylenically unsaturated carboxylic acids or the corresponding anhydrides, such as acrylic, methacrylic or maleic acids or anhydrides, fumaric acid, itaconic acid, N-methacroylalanine, N-acryloylglycine, and their water-soluble salts, monomers that are precursors of carboxylate functions, such as tert- butyl acrylate, which, after polymerization, give rise to carboxylic functions by hydrolysis, monomers having at least one sulfate or sulfonate function, such as 2-sulfooxyethyl methacrylate, vinylbenzene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), sulfoethyl acrylate or methacrylate, sulfopropyl acrylate or methacrylate, and their water-soluble salts, monomers having at least one phosphonate or phosphate function, such as vinylphosphonic acid, etc., the esters of ethylenically unsaturated phosphates, such as the phosphates derived from hydroxyethyl methacrylate (Empicryl 6835 from Rhodia) and those derived from polyoxyalkylene methacrylates, and their water-soluble salts, and 2-carboxyethyl acrylate (CEA), and mixtures thereof. In one example, the anionic monomeric unit is derived from an anionic monomer selected from the group consisting of: acrylic acid, AMPS, CEA, and mixtures thereof. In another example, the anionic monomeric unit is derived from acrylic acid. c. Cationic Monomelic Units

Non-limiting examples of cationic monomeric units suitable for the present invention include cationic monomeric units derived from cationic monomers selected from the group consisting of: N,N-(dialkylamino-ro-alkyl)amides of α,β-monoethylenically unsaturated carboxylic acids, such as Ν,Ν-dimethylaminomethylacrylamide or -methacrylamide, 2-(N,N- dimethylamino)ethylacrylamide or -methacrylamide, 3-(N,N-dimethylamino)propylacrylamide or -methacrylamide, and 4-(N,N-dimethylamino)butylacrylamide or -methacrylamide, α,β- monoethylenically unsaturated amino esters such as 2-(dimethylamino)ethyl acrylate (DMAA), 2-(dimethylamino)ethyl methacrylate (DMAM), 3-(dimethylamino)propyl methacrylate, 2-(tert- butylamino)ethyl methacrylate, 2-(dipentylamino)ethyl methacrylate, and 2(diethylamino)ethyl methacrylate, vinylpyridines, vinylamine, vinylimidazolines, monomers that are precursors of amine functions such as N-vinylformamide, N-vinylacetamide, which give rise to primary amine functions by simple acid or base hydrolysis, acryloyl- or acryloyloxyammonium monomers such as trimethylammonium propyl methacrylate chloride, trimethylammonium ethylacrylamide or - methacrylamide chloride or bromide, trimethylammonium butylacrylamide or -methacrylamide methyl sulfate, trimethylammonium propylmethacrylamide methyl sulfate, (3- methacrylamidopropyl)trimethylammonium chloride (MAPTAC), (3- methacrylamidopropyl)trimethylammonium methyl sulphate (MAPTA-MES), (3- acrylamidopropyl)trimethylammonium chloride (APTAC), methacryloyloxyethyl- trimethylammonium chloride or methyl sulfate, and acryloyloxyethyltrimethylammonium chloride; l-ethyl-2-vinylpyridinium or l-ethyl-4-vinylpyridinium bromide, chloride or methyl sulfate; Ν,Ν-dialkyldiallylamine monomers such as Ν,Ν-dimethyldiallylammonium chloride (DADMAC); polyquaternary monomers such as dimethylaminopropylmethacrylamide chloride and N-(3-chloro-2-hydroxypropyl)trimethylammonium (DIQUAT or DQ) and 2-hydroxy-N¹-(3- (2((3- methacrylamidopropyl)dimethylammino)-acetamido)propyl)-N¹, N¹, N³, N³, N³ - pentamethylpropane-l,3-diaminium chloride (TRIQUAT or TQ), and mixtures thereof. In one example, the cationic monomeric unit comprises a quaternary ammonium monomeric unit, for example a monoquaternary ammonium monomeric unit, a diquaternary ammonium monomeric unit and a triquaternary monomeric unit. In one example, the cationic monomeric unit is derived from MAPTAC. In another example, the cationic monomeric unit is derived from DADMAC. In still another example, the cationic monomeric unit is derived from TQ.

In one example, the cationic monomeric units are derived from cationic monomers selected from the group consisting of: dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth)acrylate, di-tert-butylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethylenimine, vinylamine, 2-vinylpyridine, 4- vinylpyridine and vinyl imidazole, and mixtures thereof.

In another example, the cationic monomeric units are derived from cationic monomers selected from the group consisting of: trimethylammonium ethyl (meth)acrylate bromide, chloride or methyl sulfate, trimethylammonium ethyl (meth)acrylate bromide, chloride or methyl sulfate, trimethylammonium ethyl (meth)acrylate bromide, chloride or methyl sulfate, dimethylaminoethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyl dimethylammoniumethyl (meth)acrylate bromide, chloride or methyl sulfate,, trimethylammonium ethyl (meth)acrylamido bromide, chloride, or methyl sulfate, trimethylammonium propyl (meth)acrylamido braomide, chloride, or methyl sulfate, vinyl benzyl trimethyl ammonium bromide, chloride or methyl sulfate, diallyldimethyl ammonium chloride, , l-ethyl-2-vinylpyridinium bromide, chloride or methyl sulfate, 4-vinylpyridinium bromide, chloride or methyl sulfate, and mixtures thereof.

d. Zwitterionic Monomeric Units

Non-limiting examples of zwitterionic monomeric units suitable for the present invention include zwitterionic monomeric units derived from zwitterionic monomers selected from the group consisting of: sulfobetaine monomers, such as sulfopropyl dimethylammonium ethyl methacrylate (SPE from Raschig), sulfopropyldimethylammonium propylmethacrylamide (SPP from Raschig), and sulfopropyl-2-vinylpyridinium (SPV from Raschig), 3-((3- methacrylamidopropyl)dimethylammonio)propane-l-sulfonate (SZ), phosphobetaine monomers, such as phosphatoethyl trimethylammonium ethyl methacrylate, carboxybetaine monomers, N- (carboxymethyl)-3-methacrylamido-N,N-dimethlpropan-l-aminium chloride (CZ),. In one example, the zwitterionic monomeric unit is derived from CZ, SZ, and mixtures thereof.

In one example, a polymer of the present invention may comprise at least one monomeric unit selected from groups a (nonionic monomeric units) and b (anionic monomeric units) and at least one monomeric unit selected from groups c (cationic monomeric units) and d (zwitterionic monomeric units).

In one example, the polymer comprises at least 69.9% wt and/or at least 70% wt and/or at least 75% wt and/or at least 80% wt and/or at least 85% wt and/or at least 90% wt and/or at least 95% wt and/or at least 98% wt and/or at least 99% wt and/or at least 99.5% wt of a monomeric unit from group a. The balance of the polymer (no more than 30.1% wt and/or no more than 30% wt and/or no more than 25% wt and/or no more than 20% wt and/or no more than 15% wt and/or no more than 10% wt and/or no more than 5% wt and/or no more than 2% wt and/or no more than 1% wt and/or no more than 0.5% wt total) comprises one or more monomeric units selected from groups b, c, and d. In one example, the polymer comprises from about 70% to about 99.5% wt of a monomeric unit from group a, from about 0.1% to about 10% wt of a monomeric unit from group b, and from about 0.3% to about 29% wt of a monomeric unit from group c. In still another example, the polymer comprises from about 70% to about 99.5% wt of a monomeric unit from group a, from about 0.5% to about 30% wt combined of monomeric units from groups b and c.

In one example, the polymer comprises at least 0.1% wt and/or at least 1% and/or at least 5% wt and/or at least 7% wt and/or at least 10% wt and/or to about 25% wt and/or to about 20% wt and/or to about 15% wt of a monomeric unit from group b.

In one example, polymer comprises at least 0.1% wt and/or at least 0.3% wt and/or at least 0.5% and/or at least 1% and/or at least 5% wt and/or at least 7% wt and/or at least 10% wt and/or to about 75% wt and/or to about 70% wt and/or to about 65% wt and/or to about 55% wt and/or to about 40% wt and/or to about 30% wt and/or to about 25% wt and/or to about 20% wt and/or to about 15% wt of a monomeric unit from group c.

In one example, polymer comprises at least 0.1% wt and/or at least 0.3% wt and/or at least 1% and/or at least 5% wt and/or at least 7% wt and/or at least 10% wt and/or to about 75% wt and/or to about 70% wt and/or to about 65% wt and/or to about 55% wt and/or to about 40% wt and/or to about 30% wt and/or to about 25% wt and/or to about 20% wt and/or to about 15% wt of a monomeric unit from group d.

In another example, the polymer comprises no more than 30.1% wt of a monomeric unit selected from the group consisting of: group b, group c, group d, and mixtures thereof.

In one example, the polymer may comprise a monomeric unit from group a and a monomeric unit from group b.

In one example, the polymer may comprise a monomeric unit from group a and a monomeric unit from group c.

In another example, the polymer of the present invention may comprise a monomeric unit from group a and a monomeric unit from group d.

In still another example, the polymer of the present invention may comprise a monomeric unit from group b and a monomeric unit from group c.

In still another example, the polymer of the present invention may comprise a monomeric unit from group b and a monomeric unit from group d.

In still another example, the polymer of the present invention may comprise a monomeric unit from group c and a monomeric unit from group d.

In yet another example, the polymer of the present invention may comprise a monomeric unit from group a, a monomeric unit from group b, and a monomeric unit from group c. In even another example, the polymer of the present invention may comprise a monomeric unit from group a, a monomeric unit from group b, and a monomeric unit from group d.

In yet another example, the polymer of the present invention may comprise a monomeric unit from group a, a monomeric unit from group c, and a monomeric unit from group d.

In another example, the polymer of the present invention may comprise a monomeric unit from group b, a monomeric unit from group c, and a monomeric unit from group d.

In even yet another example, the polymer of the present invention may comprise a monomeric unit from group a, a monomeric unit from group b, a monomeric unit from group c and a monomeric unit from group d.

In one example, when present in the polymer, the monomeric unit from group b and the monomeric unit from group c are present in the polymer at a molar ratio of from about 3:1 to 1:3 and/or from about 2:1 to 1:2 and/or from about 1.3:1 to 1:1.3 and/or about 1:1 or less or about 1: 1 or more.

In another example, when present in the polymer, the monomeric unit from group b and the monomeric unit from group d are present in the polymer at a molar ratio of from about 3: 1 to 1:3 and/or from about 2:1 to 1:2 and/or from about 1.3:1 to 1:1.3 and/or about 1:1 or less or about 1:1 or more.

In another example, when present in the polymer, the monomeric unit from group c and the monomeric unit from group d are present in the polymer at a molar ratio of from about 3: 1 to 1:3 and/or from about 2:1 to 1:2 and/or from about 1.3:1 to 1:1.3 and/or about 1:1 or less or about 1:1 or more.

In still another example, the polymer comprises a monomeric unit from group a and a monomeric unit from group c. For example, the polymer may comprise an acrylamide monomeric unit and a quaternary ammonium monomeric unit. The quaternary monomeric unit may be selected from the group consisting of: monoquaternary ammonium monomeric units, diquaternary ammonium monomeric units, and triquaternary ammonium monomeric units. In one example, the polymer may comprise at least 69.9% wt of the monomeric unit from group a and no more than 30.1% wt of the monomeric unit from group c.

In still another example, the polymer comprises a monomeric unit from group a and a monomeric unit from group b. For example, the polymer may comprise an acrylamide monomeric unit and an acrylic acid monomeric unit. In one example, the polymer may comprise at least 69.9% wt of the monomeric unit from group a and no more than 30.1% wt of the monomeric unit from group b. In yet another example, the polymer comprises a monomeric unit from group b and a monomeric unit from group c. For example, the polymer may comprise an anionic monomeric unit derived from an anionic monomer selected from the group consisting of: acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, carboxyethyl acrylate, and mixtures thereof and a quaternary ammonium monomeric unit. The quaternary ammonium monomeric unit may be derived from a quaternary monomer selected from the group consisting of: monoquaternary ammonium monomeric units, diquaternary ammonium monomeric units, triquaternary ammonium monomeric units, and mixtures thereof. In one example, the polymer comprises an anionic monomeric unit derived from acrylic acid and a quaternary ammonium monomeric unit derived from MAPTAC. In one example, the polymer may comprise no more than 25% wt of the monomeric unit from group b and no more than 75% wt of the monomeric unit from group c.

In even yet another example, the polymer comprises a monomeric unit from group a and a monomeric unit from group b and a monomer unit from group c. For example, the polymer may comprise an acrylamide monomeric unit, and an anionic monomeric unit derived from an anionic monomer selected from the group consisting of: acrylic acid, methacrylic acid, 2-acrylamido-2- methylpropane sulfonic acid, carboxyethyl acrylate, and mixtures thereof and a quaternary ammonium monomeric unit. The quaternary ammonium monomeric unit may be derived from a quaternary monomer selected from the group consisting of: monoquaternary ammonium monomeric units, diquaternary ammonium monomeric units, triquaternary ammonium monomeric units, and mixtures thereof. In one example, the polymer comprises a nonionic monomeric unit derived from acrylamide, an anionic monomeric unit derived from acrylic acid, and a cationic monomeric unit derived from MAPTAC. In another example, the polymer comprises a nonionic monomeric unit derived from acrylamide, an anionic monomeric unit derived from acrylic acid, and a cationic monomeric unit derived from DADMAC. In still another example, the polymer comprises a nonionic monomeric unit derived from acrylamide, an anionic monomeric unit derived from acrylic acid, and a cationic monomeric unit derived from TQ. In another example, the polymer comprises a nonionic monomeric unit derived from acrylamide, an anionic monomeric unit derived from CEA, and a cationic monomeric unit derived from MAPTAC. In still another example, the polymer comprises a nonionic monomeric unit derived from acrylamide, an anionic monomeric unit derived from AMPS, and a cationic monomeric unit derived from MAPTAC. In one example, the polymer may comprise at least 69.9% wt of the monomeric unit from group a and no more than 30.1% wt combined of the monomeric units from groups b and c. In another example, the polymer may comprise from about 70% to about 99.5% wt of the monomeric unit from group a, from 0.1% to about 30% wt of the monomeric unit from group b, and from about 0.1% to about 30% wt of the monomeric unit from group c. In still another example, the polymer may comprise from about 70% to about 99.5% wt of the monomeric unit from group a and from about 0.5% to 30% wt combined of the monomeric units from groups b and c.

In even still yet another example, the polymer comprises a monomeric unit from group a and a monomeric unit from group c and a monomer unit from group d. For example, the polymer may comprise an acrylamide monomeric unit, a quaternary ammonium monomeric unit, and a zwitterionic monomeric unit selected from the group consisting of: CZ, SZ, and mixtures thereof. The quaternary ammonium monomeric unit may be derived from a quaternary monomer selected from the group consisting of: monoquaternary ammonium monomeric units, diquaternary ammonium monomeric units, triquaternary ammonium monomeric units, and mixtures thereof. In one example, the polymer comprises a nonionic monomeric unit derived from acrylamide, a cationic monomeric unit derived from MAPTAC, and a zwitterionic monomeric unit derived from CZ. In another example, the polymer comprises a nonionic monomeric unit derived from acrylamide, a cationic monomeric unit derived from MAPTAC, and a zwitterionic monomeric unit derived from SZ. In one example, the polymer may comprise at least 69.9% wt of the monomeric unit from group a and no more than 30.1% wt combined of the monomeric units from groups c and d. In another example, the polymer may comprise from about 70% to about 99.5% wt of the monomeric unit from group a, from 0.1% to about 30% wt of the monomeric unit from group c, and from about 0.1% to about 30% wt of the monomeric unit from group d. In still another example, the polymer may comprise from about 70% to about 99.5% wt of the monomeric unit from group a and from about 0.5% to 30% wt combined of the monomeric units from groups c and d.

In even yet another example, the polymer comprises a monomeric unit from group a and a monomeric unit from group b and a monomer unit from group d. For example, the polymer may comprise an acrylamide monomeric unit, and an anionic monomeric unit derived from an anionic monomer selected from the group consisting of: acrylic acid, methacrylic acid, 2-acrylamido-2- methylpropane sulfonic acid, carboxyethyl acrylate, and mixtures thereof and a zwitterionic monomeric unit selected from the group consisting of: CZ, SZ, and mixtures thereof. In one example, the polymer comprises a nonionic monomeric unit derived from acrylamide, an anionic monomeric unit derived from acrylic acid, and zwitterionic monomeric unit derived from CZ. In another example, the polymer comprises a nonionic monomeric unit derived from acrylamide, an anionic monomeric unit derived from acrylic acid, and a zwitterionic monomeric unit derived from SZ. In one example, the polymer may comprise at least 69.9% wt of the monomeric unit from group a and no more than 30.1% wt combined of the monomeric units from groups b and d. In another example, the polymer may comprise from about 70% to about 99.5% wt of the monomeric unit from group a, from 0.1% to about 30% wt of the monomeric unit from group b, and from about 0.1% to about 30% wt of the monomeric unit from group d. In still another example, the polymer may comprise from about 70% to about 99.5% wt of the monomeric unit from group a and from about 0.5% to 30% wt combined of the monomeric units from groups b and d.

In even yet another example, the polymer comprises a monomeric unit from group a and a monomeric unit from group d. For example, the polymer may comprise an acrylamide monomeric unit, and a zwitterionic monomeric unit selected from the group consisting of: CZ, SZ, and mixtures thereof. In one example, the polymer comprises a nonionic monomeric unit derived from acrylamide and zwitterionic monomeric unit derived from CZ. In another example, the polymer comprises a nonionic monomeric unit derived from acrylamide and a zwitterionic monomeric unit derived from SZ. In one example, the polymer may comprise at least 69.9% wt of the monomeric unit from group a and no more than 30.1% wt of the monomeric unit from group d. In another example, the polymer may comprise from about 70% to about 99.5% wt of the monomeric unit from group a, from 0.5% to about 30% wt of the monomeric unit from group d.

In one example, the polymer of the present invention comprises a nonionic hydrophilic monomeric unit. Non-limiting examples of suitable hydrophilic monomeric units are derived from nonionic hydrophilic monomers selected from the group consisting of: hydroxyalkyl esters of α,β-ethylenically unsaturated acids, α,β-ethylenically unsaturated amides, α,β-ethylenically unsaturated monoalkyl amides, α,β-ethylenically unsaturated dialkyl amides, α,β-ethylenically unsaturated monomers bearing a water-soluble polyoxyalkylene segment of the poly(ethylene oxide) type, α,β-ethylenically unsaturated monomers which are precursors of hydrophilic units or segments, vinylpyrrolidones, α,β-ethylenically unsaturated monomers of the ureido type, and mixtures thereof. In one example, the nonionic hydrophilic monomeric unit is derived from acrylamide.

In another example, the polymer of the present invention comprises a nonionic hydrophobic monomeric unit. Non-limiting examples of suitable nonionic hydrophobic monomeric units are derived from nonionic hydrophobic monomers selected from the group consisting of: vinylaromatic monomers, vinyl halides, vinylidene halides, CrC₁₂ alkylesters of α,β-monoethylenically unsaturated acids, vinyl esters of saturated carboxylic acids, allyl esters of saturated carboxylic acids, α,β-monoethylenically unsaturated nitriles containing from 3 to 12 carbon atoms, a-olefins, conjugated dienes, and mixtures thereof.

In one example, the polymer comprises an anionic monomeric unit. Non-limiting examples of suitable anionic monomeric units are derived from anionic monomers selected from the group consisting of: monomers having at least one carboxylic function, for instance α,β- ethylenically unsaturated carboxylic acids or the corresponding anhydrides, monomers that are precursors of carboxylate functions, monomers having at least one sulfate or sulfonate function, monomers having at least one phosphonate or phosphate function, esters of ethylenically unsaturated phosphates, and mixtures thereof. In one example, the anionic monomeric unit is derived from an anionic monomer selected from the group consisting of: acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, carboxyethyl acrylate, and mixtures thereof.

In one example, the polymer comprises a cationic monomeric unit. Non-limiting examples of suitable cationic monomeric units are derived from cationic monomers selected from the group consisting of: acryloyl- or acryloyloxyammonium monomers, l-ethyl-2- vinylpyridinium or l-ethyl-4-vinylpyridinium bromide, chloride or methyl sulfate, N,N- dialkyldiallylamine monomers, polyquatemary monomers, N,N-(dialkylamino-ro-alkyl)amides of α,β-monoethylenically unsaturated carboxylic acids, α,β-monoethylenically unsaturated amino esters, vinylpyridines, vinylamine, vinylimidazolines, monomers that are precursors of amine functions which give rise to primary amine functions by simple acid or base hydrolysis, and mixtures thereof. In one example, the cationic monomeric unit is derived from MAPTAC. In another example, the cationic monomeric unit is derived from DADMAC. In still another example, the cationic monomeric unit is derived from 2-hydroxy-N¹-(3-(2((3- methacrylamidopropyl)dimethylammino)-acetamido)propyl)-N¹, N¹, N³, N³, N³ pentamethylpropane- 1 ,3 -diaminium chloride.

In one example, the soil capture agents are water-soluble.

The soil capture agents may be made by any suitable process known in the art. For example, the soil capture agent polymers may be made by radical polymerization.

The soil capture agent polymers of the present invention can be made by a wide variety of techniques, including bulk, solution, emulsion, or suspension polymerization. Polymerization methods and techniques for polymerization are described generally in Encyclopedia of Polymer Science and Technology, Interscience Publishers (New York), Vol. 7, pp. 361-431 (1967), and Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, Vol 18, pp. 740-744, John Wiley & Sons (New York), 1982, both incorporated by reference herein. See also Sorenson, W. P. and Campbell, T. W., Preparative Methods of Polymer Chemistry. 2nd edition, Interscience Publishers (New York), 1968, pp. 248-251, incorporated by reference herein, for general reaction techniques suitable for the present invention. In one example, the polymers are made by free radical copolymerization, using water soluble initiators. Suitable free radical initiators include, but are not limited to, thermal initiators, redox couples, and photochemical initiators. Redox and photochemical initiators may be used for polymerization processes initiated at temperatures below about 30°C (86°F). Such initiators are described generally in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, John Wiley & Sons (New York), Vol. 13, pp. 355- 373 (1981), incorporated by reference herein. Typical water soluble initiators that can provide radicals at 30°C or below include redox couples, such as potassium persulfate/silver nitrate, and ascorbic acid/hydrogen peroxide. In one example, the method utilizes thermal initiators in polymerization processes conducted above 40°C (104°F). Water soluble initiators that can provide radicals at 40°C (104°F) or higher can be used. These include, but are not limited to, hydrogen peroxide, ammonium persulfate, and 2,2'-azobis(2-amidinopropane) dihydrochloride. In one example, water soluble starting monomers are polymerized in an aqueous alcohol solvent at 60°C (140°F) using 2,2'-azobis(2-amidinopropane) dihydrochloride as the initiator. The solvent should typically contain at least about 10% by volume, of alcohol in order to prevent the polymerization reaction medium from gelling. Suitable alcohols for use in such reaction include low molecular weight alcohols such as, but not limited to, methanol, ethanol, isopropanol, and butanol.

Another technique is a solution polymerization as described in U.S. Pat. No. 3,317,370, Kekish, issued May 2, 1967 and U.S. Pat. No. 3,410,828, Kekish, issued Nov. 12, 1968, both incorporated herein by reference. According to such process, the acrolein, or other aldehydic monomer, is copolymerized with a non-nucleophilic, water soluble, nitrogen-heterocyclic polymerizable monomer and a redox initiator system. The copolymer is then made cationic by reacting the copolymer with a water soluble amine or amine quaternary. Amines, including amine quaternaries, that are useful include, but are not limited to, primary, secondary, and tertiary amines such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, or partial or fully quaternized derivatives of any of the foregoing, hydrazides and quaternaries thereof such as betaine hydrazide chloride, N-N-dimethylglycine hydrazide, unsymmetrical dimethyl hydrazides, polymers, such as those formed by reaction of urea and polyalkylene polyamines, guanidines, biguanides, guanylureas, mono and polyhydroxy polyamines and quaternaries thereof, etc. When using this emulsion copolymerization technique, it will be necessary to control molecular weight to within the ranges provided herein. Methods for Forming the Laminate Cleaning Implements

The methods of forming the tufted laminate webs as in FIGS. 1-4 and 7-10 and the indented laminate web as in FIGS. 5-6 involve subjecting the sheet(s) and the substrate to at least one cycle or pass through a mechanical deformation process.

The mechanical deformation process can be carried out on any suitable apparatus that may comprise any suitable type(s) of forming members. Suitable types of forming apparatus include, but are not limited to: a pair of rolls that define a nip therebetween; pairs of plates; conveyors with pucks (or small plates) that define a nip therebetween; belts that define a nip therebetween; or combinations thereof. Examples of belts and rolls that could be modified for use in the present methods are described in U.S. Pat. No. 8,021,591.

FIG. 11 is a perspective view of an apparatus for forming the web for use in the present invention. The apparatus 200 comprises a pair of intermeshing rolls 202 and 204, each rotating about an axis A, the axis A being parallel in the same plane. Roll 202 comprises a plurality of ridges 206 and corresponding grooves 208 which extend unbroken about the entire circumference of roll 202. Roll 204 is similar to roll 202, but rather than having ridges that extend unbroken about the entire circumference, roll 204 comprises a plurality of rows of circumferentially- extending ridges that have been modified to be rows of circumferentially- spaced teeth 210 that extend in spaced relationship about at least a portion of roll 204. The individual rows of teeth 210 of roll 204 are separated by corresponding grooves 212. In operation, rolls 202 and 204 intermesh such that the ridges 206 of roll 202 extend into the grooves 212 of roll 204 and the teeth 210 of roll 204 extend into the grooves 208 of roll 202. Both or either of rolls 202 and 204 can be heated by means known in the art such as by using hot oil filled rollers or electrically- heated rollers.

In FIG. 11, the apparatus 200 is shown in a configuration having one patterned roll, e.g., roll 204, and one non-patterned grooved roll 202. However, in certain embodiments it may be preferable to use two patterned rolls 204 having either the same or differing patterns, in the same or different corresponding regions of the respective rolls. Such an apparatus can produce webs with tufts protruding from both sides of the laminate web.

The laminate web can be made by mechanically deforming sheets and/or a substrate, which can each be described as generally planar and two-dimensional prior to processing by the apparatus shown in FIG. 11. By "planar" and "two-dimensional" is meant simply that the webs start the process in a generally flat condition relative to the finished web that has distinct, out-of- plane, Z-direction three-dimensionality due to the formation of textured portions, such as tufts 226. "Planar" and "two-dimensional" are not meant to imply any particular flatness, smoothness or dimensionality.

The sheet(s) and substrate are moved in the machine direction to the nip 216 of counter- rotating intermeshing rolls 202 and 204. The sheet(s) and substrate can be held in at a sufficient tension so as to enter the nip 216 in a generally flattened condition by means well known in the art of web handling. As each sheet(s) and substrate goes through the nip 216 the teeth 210 of roll 204 which are intermeshed with grooves 208 of roll 202 can simultaneously urge portions of sheet(s) and substrate out of the plane to form tufts 226. In one example, the teeth 210 in effect "push" or "punch" fibers of both the facing sheet and/or the backing sheet out of plane to form tufts. In another example, the teeth 210 in effect "push" or "punch" fibers of backing sheet and/or the substrate through the facing sheet. Fibers can be urged out of plane due to fiber mobility, or they can be urged out of plane by being stretched and/or plastically deformed in the Z-direction. In another example, the teeth 210 of roll 204 do not "punch" through sheet(s) and the substrate and essentially deform the web.

The number, spacing, and size of tufts can be varied by changing the number, spacing, and size of teeth 210 and making corresponding dimensional changes as necessary to roll 204 and/or roll 202. This variation, together with the variation possible in sheet(s) and the substrate permits many varied laminate webs for use in a laminate cleaning implement.

Additional information on mechanically deforming laminates, sheets, and substrates are disclosed in U.S. Pat. Nos. 5,518,801 and 7,670,665 and U.S. Pat. App. No. 13/455,698. The laminates, sheets, and substrates can also be deformed multiple times using the process described in U.S. Pat. App. No. 13/094,206.

Test Methods

Consumption Rate Test

To measure the Consumption Rate of a laminate cleaning implement, use a rotary tumbler

(Lortone, Inc., Seattle, Wash., USA model 33B or equivalent) with 4 in. diameter by 4 in. deep cylindrical rubber housing having 825 cc internal volume. The housing revolves on the tumbler at 43 rpm. Obtain a supply of tap water at about 7.5 grains water hardness and conductivity between 100 to not more than 400 microSemens per centimeter ^S/cm) and heat in a reservoir beaker to 45 °C. Maintain the water supply at the target temperature within 1 degree for the test duration. Add 200.0 g water from the reservoir to the housing. Weigh a laminate cleaning implement to obtain the initial weight, and add the laminate cleaning implement to the housing. Seal the housing with its accompanying watertight lid and place the sealed housing onto the rotary tumbler for exactly 3 minutes. Remove the housing, remove the housing lid, and retrieve the laminate cleaning implement. Stir the remaining water in the housing for a few seconds and measure its conductivity and temperature using a Mettler Toledo Seven multimeter with InLab 740 probe or equivalent. Dry the laminate cleaning implement surface by pressing, not rubbing, using paper towels with light hand pressure for about 30 seconds, until it is dry to the touch and transfers no more visible water to a dry paper towel using the same pressure at any point on its surface or edges. If the laminate cleaning implement transfers partially dissolved or dissolving components in addition to liquid water, for example if the substrate is a composition similar to conventional bar soap it may transfer paste-like material, the transferred components are to be removed and the laminate cleaning implement is considered dry when visible transfer is no longer evident. Weigh the laminate cleaning implement.

Empty and rinse the housing in hot tap water and dry it to complete 1 cycle. Repeat the cycle with the same laminate cleaning implement 4 more times for a total of 5 cycles. Measure the conductivity of the water reservoir at 30 °C, 35 °C, 40 °C, and 45 °C. Using a new laminate cleaning implement that is the same as the first one, prepare a 1% solution by removing 1.00 g of its substrate and adding it to 99.00 grams of water from the reservoir. Dissolve the substrate completely, using agitation and heat as necessary. Measure conductivity of the 1% solution at the same 4 temperatures. Prepare a 2% solution in the same way (2.00 grams substrate in 98.00 grams water), and measure its conductivity at the same 4 temperatures. Regress the conductivity vs. temperature results for each solution (0%, 1%, and 2%) and obtain the algebraic expressions for each.

For each conductivity-temperature datum for the water in the housing obtained during the each cycle, calculate the regressed conductivity for the 0%, 1% and 2% solutions at the temperature measured by the InLab 470 probe for each cycle. Execute a second set of linear regressions for each temperature obtained in the cycles using the solution concentrations (0%, 1% and 2%) as the y (output) and the regressed conductivity values as x (input). Use this second regression at each temperature obtained in each cycle with its paired conductivity value obtained as the input value for x to obtain y, which is the amount of solids of the laminate cleaning implement dissolved for each cycle. Add the dissolved solids for the 5 cycles and divide by 5 to obtain the Average Dissolved Solids. Multiply the value by 1.67 to obtain the consumption rate of the laminate cleaning implement.

Dissolution Test Method

Apparatus and Materials:

600 mL Beaker

Magnetic Stirrer (Labline Model No. 1250 or equivalent) Magnetic Stirring Rod (5 cm)

Thermometer (1 to 100°C +/- 1 °C)

Template, Stainless Steel (3.8 cm x 3.2 cm)

Timer (0-300 seconds, accurate to the nearest second)

35 mm Slide Mount having an open area of 3.8 cm x 3.2 cm (commercially available from Polaroid Corporation)

35 mm Slide Mount Holder

City of Cincinnati Water or equivalent having the following properties: Total Hardness = 155 mg/L as CaC03; Calcium content = 33.2 mg/L; Magnesium content = 17.5 mg/L; Phosphate content = 0.0462

Sample Preparation:

1. Cut 3 test samples from a substrate to be tested ("sample") using the template to ensure that the sample fits within the 35 mm slide mount with open area dimensions 24 x 36 mm (i.e. 3.8 cm x 3.2 cm specimen). Cut the samples from areas of the substrate equally spaced along the transverse direction of the dissolvable film substrate or the dissolvable filament substrate. As one of ordinary skill in the art would know, the basis weight of the sample is measured and the sample weight is determined by utilizing the open area dimensions.

2. Lock each of the 3 samples in a separate 35 mm slide mount.

3. Place magnetic stirring rod into the 600 mL Beaker.

4. Obtain 500 mL or greater of Cincinnati city water and measure water temperature with thermometer and, if necessary, adjust the temperature of the water to maintain it at the testing temperature; namely, 5°C. Once the water temperature is at 5°C, fill the 600 mL beaker with 500 mL of the water.

5. Next, place the beaker on the magnetic stirrer. Turn the stirrer on, and adjust stir speed until a vortex develops in the water and the bottom of the vortex is at the 400 mL mark on the 600 mL beaker.

6. Secure the 35 mm slide mount with sample locked therein in a holder designed to lower the 35 mm slide mount into the water in the beaker, for example an alligator clamp of a 35 mm slide mount holder designed to position the 35 mm slide mount into the water present in the 600 mL beaker. The 35 mm slide mount is held by the alligator clamp in the middle of one long end of the 35 mm slide mount such that the long ends of the 35 mm slide mount are parallel to the surface of the water present in the 600 mL beaker. This set up will position the film or nonwoven surface perpendicular to the flow of the water. A slightly modified example of an arrangement of a 35 mm slide mount and slide mount holder are shown in FIGS. 1-3 of U.S. Patent No. 6,787,512.

7. In one motion, the 35 mm slide mount holder, which positions the 35 mm slide mount above the center of the water in the beaker, is dropped resulting in the 35 mm slide mount becoming submerged in the water sufficiently such that the water contacts the entire exposed surface area of the film or nonwoven sample locked in the 35 mm slide mount. As soon as the water contacts the entire exposed surface area of the film or nonwoven start the timer. Disintegration occurs when the film or nonwoven breaks apart. When all of the visible film or nonwoven is released from the slide mount, raise the 35 mm slide mount out of the water while continuing to monitor the water for undissolved film or nonwoven fragments. Dissolution occurs when all film or nonwoven fragments are no longer visible in the water.

8. Three replicates of each sample are run.

9. Each disintegration and dissolution time is normalized by weight of the sample to obtain values of the disintegration and dissolution times per g of sample tested, which is in units of seconds/gram of sample (s/g). The average disintegration and dissolution times per g of sample tested of the three replicates are recorded. As one of ordinary skill in the art would know, the disintegration time and dissolution time for each sample is also recorded.

Charge Density Test Method

The charge density of a polymer, such as a soil adsorption polymer, can be determined by using a Mutek PCD-04 Particle Charge Detector available from BTG, or equivalent instrument. The following guidelines provided by BTG are used.

Start with a 0.1% solution (0.1 g polymer + 99.9 g deionized water) (sample). Depending on the titrant consumption increase or decrease polymer content if needed. Solution pH is adjusted prior to final dilution as charge density of many polymers and/or additives is dependent upon solution pH. A pH of 4.5 is used here.

1. Place 20 mL of sample in the PCD measuring cell and insert piston.

2. Put the measuring cell with piston and sample in the PCD, the electrodes are facing the rear. Slide the cell along the guide until it touches the rear.

3. Pull piston upwards and turn it counter-clock-wise to lock the piston in place.

4. Switch on the motor. The streaming potential is shown on the touch panel. Wait 2 minutes until the signal is stable. 5. Use an oppositely charged titrant (for example for a cationic sample having a positive streaming potential: use an anionic titrant). Titrants are available from BTG consisting of 0.001N PVSK or 0.001N PolyDADMAC.

6. An automatic titrator available from BTG is utilized. After selecting the proper titrant, set the titrator to rinse the tubing by dispensing 10 mL insuring that all air bubbles have been purged.

7. Place tubing tip below the surface of the sample and start titration. The automatic titrator is set to stop automatically when the potential reaches 0 mV.

8. Record consumption of titrant, ideally, the consumption of titrant should be 0.2 mL to 10 mL; otherwise decrease or increase polymer content.

9. Repeat titration of a second 20 mL aliquot of the polymer sample.

10. Calculate charge demand (solution) or charge demand (solids);

Charge demand (eq/L) = V titrant used(L) x Cone, of titrant in Normality (eq/L)

Volume of sample titrated (L)

Charge demand (eq/g) = V titrant used(L) x Cone, of titrant in Normality (eq/L)

Wt. solids of the sample or its active substance (g) The charge demand (charge density) of a polymer is reported in meq/g units.

Gas Pycnometry Method

The Percent Open Cell Content is measured via gas pycnometry. Gas pycnometry is a common analytical technique that uses a gas displacement method to measure volume accurately.

Inert gases, such as helium or nitrogen, are used as the displacement medium. The sample is sealed in the instrument compartment of known volume, the appropriate inert gas is admitted, and then expanded into another precision internal volume. The pressure before and after expansion is measured and used to compute the sample volume. Dividing this volume into the sample weight gives the gas displacement density.

The percentage of open cells can be determined by performing a test which uses Micromeritics® AccuPyc Pycnometer. The ASTM procedure D2856 describes 5 methods (A, B,

C, D, and E) for determining the percent of open cells of foam materials.

For these experiments, the samples can be analyzed using an Accupyc 1340 using nitrogen gas with the ASTM foampyc software. Method C of the ASTM procedure is to be used to calculate to percent open cells. This method simply compares the geometric volume as determined using calipers and standard volume calculations to the true volume as measured by the Accupyc. It is recommended that these measurements be conducted by Micromeretics® Analytical Services, Inc. (One Micromeritics Dr, Suite 200, Norcross, GA 30093). More information on this technique is available in "Analytical Methods in Fine particle Technology", by Clyde Orr and Paul Webb.

Specific Surface Area Method

The Specific Surface Area of a substrate that comprise an open cell foam is measured via a gas adsorption technique. Surface Area is a measure of the exposed surface of a solid sample on the molecular scale. The BET (Brunauer, Emmet, and Teller) theory is the most popular model used to determine the surface area and is based upon gas adsorption isotherms. Gas Adsorption uses physical adsorption and capillary condensation to measure a gas adsorption isotherm. The technique is summarized by the following steps; a sample is placed in a sample tube and is heated under vacuum or flowing gas to remove contamination on the surface of the sample. The sample weight is obtained by subtracting the empty sample tube weight from the degassed sample+sample tube weight. The sample tube is then placed on the analysis port and the analysis is started. The first step in the analysis process is to evacuate the sample tube, followed by a measurement of the free space volume in the sample tube using helium gas at liquid nitrogen temperatures. The sample is then evacuated a second time to remove the helium gas. The instrument then begins collecting the adsorption isotherm by dosing krypton gas at user specified intervals until the requested pressure measurements are achieved.

Sample Preparation (Degassing): A sample not adequately cleaned of adsorbed contaminants will outgas during an analysis and some portion of the surface will be inaccessible to measurement. The purpose of degassing is to remove these adsorbed molecules from the surface of the sample prior to analysis. Adsorptive molecules must reach all parts of the surface for the true surface area to be revealed. Samples are prepared by heating the sample while simultaneously evacuating the sample tube.

For these experiments, the samples are outgassed under evacuation at room temperature overnight. Samples may then analyzed using an ASAP 2420 with krypton gas adsorption. Krypton gas is preferred over nitrogen gas as it has a saturation pressure approximately 1/300 that of nitrogen at liquid nitrogen temperature (krypton: 2 .5 ton; nitrogen: 760 ton). Therefore, compared to nitrogen, there is in the free space above the sample 1/300 the number of krypton molecules present at the same relative pressure. Since the same number of krypton and nitrogen molecules are required to form a monolayer, this number represents a far greater proportion of the quantity dosed than in the case of nitrogen. These measurements can be conducted by Micromeretics® Analytical Services, Inc. (One Micromeritics Dr, Suite 200, Norcross, Ga. 30093). More information on this technique is available in "Analytical Methods in Fine particle Technology", by Clyde Orr and Paul Webb.

Water Content Test Method

The water (moisture) content present in a filament and/or fiber and/or substrate is measured using the following Water Content Test Method.

A substrate or portion thereof ("sample") is placed in a conditioned room at a temperature of 73°F ± 4°F (about 23°C ± 2.2°C) and a relative humidity of 50% ± 10% for at least 24 hours prior to testing. The weight of the sample is recorded when no further weight change is detected for at least a 5 minute period. Record this weight as the "equilibrium weight" of the sample. Next, place the sample in a drying oven for 24 hours at 70°C with a relative humidity of about 4% to dry the sample. After the 24 hours of drying, immediately weigh the sample. Record this weight as the "dry weight" of the sample. The water (moisture) content of the sample is calculated as follows:

% Water (moisture) in sample = 100% x (Equilibrium weight of sample - Dry weight of sample)

Dry weight of sample

The % Water (moisture) in sample for 3 replicates is averaged to give the reported % Water (moisture) in sample.

Values disclosed herein as ends of ranges are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each numerical range is intended to mean both the recited values and any integers within the range. For example a range disclosed as "1 to 10" is intended to mean "1, 2, 3, 4, 5, 6, 7, 8, 9, 10."

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While particular examples of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

CLAIMS What is claimed is:

1. A laminate cleaning implement comprising:

a. a facing sheet;

b. a backing sheet; and c. a substrate comprising an active agent wherein the substrate is disposed between the facing sheet and the backing sheet and wherein upon exposure to conditions of intended use the active agent is released;

wherein the facing sheet and the substrate are mechanically intermeshed to provide one or more discrete tufts protruding outwardly from the facing sheet and wherein the tufts comprise a portion of the substrate.

2. The laminate cleaning implement of Claim 1 wherein the backing sheet is water

impermeable.

3. The laminate cleaning implement of any of the preceding claims further comprising a water impermeable sheet.

4. The laminate cleaning implement of any of the preceding claims wherein the tufts further comprise distally-disposed melt-bonded portions.

5. The laminate cleaning implement of any of the preceding claims wherein the cleaning implement further comprises one or more surface melt-bonded portions wherein the surface melt-bonded portions are substantially surface bonded.

6. The laminate cleaning implement of any of the preceding claims wherein the cleaning implement further comprises one or more surface melt-bonded portions wherein the surface melt-bonded portions substantially bond the facing sheet and the backing sheet and the substrate is displaced out of the surface melt-bonded portions.

7. The laminate cleaning implement of any of the preceding claims wherein the cleaning implement has a consumption rate of 3 g/use to 30 g/use.

8. The laminate cleaning implement of any of the preceding claims wherein upon exposure to conditions of intended use the substrate lathers.

9. The laminate cleaning implement of any of the preceding claims wherein the substrate comprises less than or equal to 10% moisture.

10. The laminate cleaning implement of any of the preceding claims wherein the substrate dissolves in less than 60 seconds per gram.

11. The laminate cleaning implement of any of the preceding claims wherein the substrate is an open cell foam with a percent open cell content of from 80% to 100%.

12. The laminate cleaning implement of any of the preceding claims wherein the substrate is an open cell foam with a specific surface area of from 0.03 m²/g to 0.25 m²/g.

13. The laminate cleaning implement of any of the preceding claims wherein the active agent is selected from the group consisting of conditioning agents, surfactants, skin cleansing agents, skin care agents, moisturizers, protectants, barrier materials, smoothing agents, lubricants, fabric softening agents, fabric care stain removal agents, soil release agents, dishwashing agents, hard surface cleansing agents, bleaching agents, carpet care agents, make-up removal agents, deposition aids, perfumes, odor absorbing agents, tooth care agents, ear care agents, and mixtures thereof.

14. The laminate cleaning implement according to any of the preceding claims wherein the laminate cleaning implement further comprises a soil capture agent, preferably wherein the soil capture agent is present on the facing sheet.