WO2000029209A1

WO2000029209A1 - A flexible mat for absorbing liquids comprising polymeric foam materials

Info

Publication number: WO2000029209A1
Application number: PCT/US1999/026337
Authority: WO
Inventors: Jonnie Pehrson Conrad; John Collins Dyer; Thomas C. Hortel; Roxanne Drago Westendorf
Original assignee: The Procter & Gamble Company
Priority date: 1998-11-12
Filing date: 1999-11-08
Publication date: 2000-05-25
Also published as: CA2348462A1; AU1611700A; JP2002529286A; US6245697B1; MXPA01004809A; EP1128959A1; PE20000924A1

Abstract

Disclosed are protective, flexible mats for absorbing liquids on floors and other surfaces which contain a waterproof component and a polymeric foam sheet formed by polymerizing a high internal phase water-in-oil emulsion. The mats can also contain a non-skid material and/or at least one liquid pervious sheet. The mats are suitable for absorbing hydrophilic and hydrophobic liquids.

Description

A FLEXIBLE MAT FOR ABSORBING LIQUIDS COMPRISING POLYMERIC FOAM MATERIALS

FIELD OF THE INVENTION The present invention relates to a protective, flexible, absorbent mat which is used on floors and other surfaces. BACKGROUND OF THE INVENTION

The protection of surfaces such as floors, carpets, rugs, furniture, upholstery and other surfaces is of significant commercial interest. Similarly of interest are examples wherein the direction of the protection is reversed, e.g., to protect an item or person from contamination by the environment. Protective coverings including films, towels, rugs and other woven or nonwoven fabπcs both disposable and non-disposable have been widely used. Generally, these materials are not satisfactory in all respects. For example, many provide inadequate fluid absorbency and cannot soak up and retain spilled fluids. Others tear or abraid easily and generally lack the necessary mechanical strength for use. Still others are expensive and may require laundering and reuse. Some constructions lack sufficient stability when exposed to light, radiation, or certain chemicals which may further limit their utility.

Mats which contain a foam or cellular polymer, such as are described m "Polymer Foams", ACS Symposium Seπes 669, Khemam, K. C, Ed.; American Chemical Society, Washington, DC, 1997, are well known m the art. For example, U.S. 4,822,669 (Roga) issued Apπl 18, 1987, discloses a low cost absorbent mat having a top layer of nonwoven fiber laminated with a water impervious film and a bottom layer of polvurethane foam. The function of the foam m this instant appears to relate to providing a resilient mat for comfort reasons. The foam further provides a nonskid bottom surface. U.S. 45,028,468 (Taylor) issued July 2, 1991 discloses a surgical mat with disposable cover for use in an operating room having a resilient or foam mateπal to reduce fatigue of the user. U.S. 5,658,637 (Volz) issued August 2. 1995 discloses a slip-resistant washable floor mat suitable for use in motor vehicles having a layer of coarse-celled polyurethane foam. Other similar references mclude U.S. 3,856,610 (Bruneel) issued December 24, 1974, U.S. 4.421,809 (Bish et al.) issued December 20, 1983, U.S. 4.143,194 (Wihksne) issued March 6, 1979, U.S. 4,285,075 (Nelson) issued August 15. 1981, and U,S, 4,609,580 (Rockett et al.) issued September 2, 1986. The citattons m this paragraphs are all incorporated herein by reference.

The use of an absorbent foam in such an article would be useful m that it could both provide for absorbency of contacted (spilled) liquids while also conferπng a cushioning benefit. This could further extend the utility of such mats to mclude spill wipe up in addition to protection. Articles containing absorbent foams are also known. One type of absorbent foam is prepared by polymeπzmg High Internal Phase Emulsions (hereafter referred to as "HIPEs")- Such foams (hereinafter referred to as HIPE foams) are descπbed m, for example, U.S. Patent No. 5.260,345 (DesMarais et al.) issued November 9, 1993. U.S. Patent No. 5,268,224 (DesMarais et al.) issued December 7, 1993, U.S. 5,387,207 (Dyer et al.) issued February 7, 1995, and U.S. Patent No. 5,650,222 (DesMarais et al) issued July 22, 1997, (each of which is incorporated herein by reference). Absorbent articles made using such HIPE foams for mopping up household spills are known in the art and mclude U.S. Patent 4,606,958 (Haq et al.) issued August 19, 1986. Surgical drapes and bandages can also be formed from HIPE-foams modified to absorb blood, as descπbed in U.S. 5,795,921 (Dyer et al.) issued August 18, 1998. HIPE-foams offer the advantage of high absorbent capacity and fluid retention. However, these foams are typically not durable enough to be used alone and must be incorporated in a substrate or other non- polymeπc foam mateπal to be of benefit. U.S. patent application Seπal No. 60/077,955 (DesMarais et al.), filed March 13, 1998 (P&G Case 7055P) discloses a version of these HIPE foams having extraordinary toughness and strength relative to previous versions. Absorbent foams other than HIPE foams are well known in the art. However, such foams lack the necessary fine microstructure to hold fluids effectively. Mats made using such foams, for example, polyurethane foams, will drain if lifted in a vertical position. Further, polyurethane foams are not sufficiently stable with respect to exposure to light to be universally useful without unsightly yellowing.

SUMMARY OF THE INVENTION The present invention encompasses a flexible mat for absorbing liquids for use on floors and other surfaces compπsmg: a) a waterproof backing layer or treatment; b) a HIPE foam sheet formed by polymenzation of water-m-oil emulsion having:

1 ) an oil phase comprising: a) from about 85 to about 98%, by weight of the oil phase, said monomer component comprising: i) from about 45 to about 70%, by weight of the monomer component, of a substantially water-insoluble, monofunctional monomer capable of forming a homopolymer having a Tg of about 25°C or less; ii) from about 25 to about 45%, by weight of. the monomer component, of a substantially water-insoluble, monofunctional comonomer capable of imparting toughness about equivalent to that provided by styrene; iii) from about 3 to about 25%, by weight of the monomer component, of a first substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of divinylbenzenes and analogs thereof; iv) from 0 to about 15%, by weight of the monomer component, of a second substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of polyfunctional acrylates, methacrylates, acrylamides, methacrylamides, and mixtures thereof; v) wherein the weight ratio of the monofunctional comonomer capable of imparting toughness (ii) to the sum of the first and second polyfunctional crosslinking agents (iii + iv) is at least about 1: 1; b) from about 2 to about 15%, by weight of the oil phase, of an emulsifier component which is soluble in the oil phase and which is suitable for forming a stable water-in-oil emulsion; and

2) a water phase compπsing from about 0.1 to about 20%, by weight of the water phase, of a water-soluble electrolyte; and

3) a volume to weight ratio of water phase to oil phase of at least about 12: 1.

The mats can optionally contain optional components such as at least one liquid pervious sheet, and a non-skid material.

All percentages, ratios and proportions herein are by weight, unless otherwise specified. All documents cited are, in relevant part, incorporated herein by reference.

BRIEF DESCRIPTION OF THE DRAWING Figure 1 of the drawings is a scanning electron micrograph (hereinafter "SEM") (3 Ox magnification) of a cut section of a representauve polymerrc foam useful m the present mvenπon according to Example I, Table 1. Number 1

Figures 2 and 3 of the drawings are photomicrographs (lOOx magnification) of the foam of Figure 1

Figure 4 of the drawings is a photomicrograph (lOOOx) of the foam of Figure 1.

DETAILED DESCRIPTION OF THEINVENTION A cπtical component of the protective, semi-durable, absorbent mat herein compπses a flexible and absorbent HIPE foam, typically m sheet form. The flexibility of the HTPE foam is desired for both ease of use (conformabihty) and comfort (as when a user stands, sits, or kneels on the mat) Flexibility deπves from the thickness of the sheet, its vaπous components including the HLPE foam, and the glass transition temperature or Tg of the HIPE foam. To confer flexibility, it is generally preferred that the Tg of the HIPE foam be near or below the temperature of intended use However, m some cases a sttffer mat may be desired wherein the Tg is higher than the temperature of intended use.

The HIPE foam may be surface treated so as to render it hydrophihc and absorbent with respect to aqueous fluids. Since the chemical composition of the polymeπc foam typically renders it highly pophilic as well, the polymeπc foam can provide both hydrophihcity and lipophilicity simultaneously Such duality is generally preferred for broadest utility, though in specific instances the hydrophihcity may not be desired. HIPE foams typically have a generous absorbent capacity, e.g., relatively little foam is needed to absorb a relatively large amount of liquid, usually expressed m terms of g/g capacity Also, the HIPE foam can imbibe the liquid quickly and completely. This is achieved by a combination of modification of the cell sizes of the foam and the hydrophihcity of the surface. Further, the HIPE foam will retain the imbibed fluid better than other mateπals including other absorbent foams when the sheet is transposed into the vertical dimension or when another mateπal (such as the knee of the user) is placed on the surface of the mat.

The HIPE foam of the current invention may be sliced to provide a sheet of relatively thin mateπal for incorporation into the mat T e thickness of such slices will typically be between about 0.5 mm and 5 mm, preferably between about 1.5 mm and 3 mm, such a range generally found to provide sufficient absorbent capacity and mechanical strength while also being flexible and easy to slice. The HJJPE foam may also be used m a "thin-until-wet" state as descπbed in U.S. 5,387,207, supra. The HLPE foam may also have heterogeneous character as descπbed more fully m U.S. 5,817.704 (Shiveley et al.) issued October 6, 1998, incorporated herein by reference For example, mats made from such heterogeneous HLPE foams may be πgid in more region or regions and flexible m yet others so as to provide conformity to a particular predetermined shape or location and use Similarly, the mat made from these foams may be hydrophihc in the mteπor region and hydrophobic near the edges so as to reduce edge leakage of the product Additionally, it may be useful to form the mats of the present mventton wherein two or more sheet of HIPE foam are layered within the product For example, an upper layer may compπse larger-celled foams which are preferred for rate of fluid imbibition. The lower layer may then compπse smaller-celled foams which are preferred for tenacity of fluid holding. In a preferred embodiment, such a design provides a mat which remams substantially dry to the touch even when it contains a relatively high level of liquid This can be especially useful wherein the mat is used in a door way or m an automobile because the users shoes will not track wetness into other areas past the mat itself In previous protective mats, this often is a problem once the mat absorbs even relatively small amounts of liquid In the present invention, the thickness of the polymeπc foam sheet can be vaπed within an individual sheet thereby providing an additional physical barπer for spill control and protection For example, the outer edges of the polymeπc foam sheet could be formulated to be thicker than the internal portion of the sheet to provide for containment of fluids until they are fully absorbed by the mat The mat of the present invention can be a single piece of polymeπc foam sheet shaped as desired or needed to best fit the end use The mat can also compπse more than one polymeπc foam sheet that can be adhesively bonded or otherwise linked together to deliver the desired size. Furthermore, the mat can be cut by the user to a desired shape and size. It is also envisioned that the mats could be manufactured with perforations or other divisions thereby allowing the user to easily choose a desired size based on his/her need at the time of use The mat may also be specifically cut for special uses, such as, for example, shoe and boot inserts As stated above, the mats of the present mvennon can be made to any size which will meet the needs of the user. Particularly useful are mats having the following dimensions- 5" x 5", 8" x 10", 11" x 11", 15" x 19", 24" x 36", 36" x 60", and the like

I Uses

The mats of the present invention are very versatile and incorporate a wide vaπety of uses including, protecting surfaces from water, ra , moisture, dirt, mud, bodily fluids (including blood, mucous, feces, and the like), oil, grease, transmission and brake fluid, and other hydrophihc or hydrophobic liquids. These mats can be used, for example, outdoors, m shoes and boots, m homes, garages, repair shops, automobiles, offices, vending machine areas, kitchens, refrigerators, under defrosting foods, restaurants, schools, surgeπes. emergency rooms, athletic and fitness facilities, showers, schools, health care facilities, in the cleaning up of spills, especially large volume spills, and m industry The user benefits of mats include protection of durable surfaces, i.e., lower frequency of professional cleaning, prevention of damage, maintenance of appearance/function of surfaces so as to increase useable life, large spill wipe-up, and reduction of food losses that can be caused by contamination from leaking meats and vegetables. As discussed above, the size, shape, and thickness of these mats can be modified based on the desired end use of the article. Accordingly, the following is a non miting list of potential uses for mats of the present invention door mats for wet/muddy/dirty feet, pets, umbrellas, snow, etc.; shoe inserts; car seat and carpet protectors; car trunk liners; under a child's high chair; under chair/table while child or adult is doing crafts; under baby duπng diaper changing; in front of or under sinks; under or in front of appliances which may leak or overflow; in the refrigerator as a shelf lmer or under thawing meats; in the pantry under oil containers; m the garage for oil, gas leaks and spills: under houseplants; under pet's food/water bowls; under litter boxes; as pet cage liners; as a protective throw for bedwett g or incontinence; spill clean ups; bath mats; around the toilet; as a stadium cushion or blanket to protect from wet surfaces and insulate; disposable, absorbent coasters and place mats; in food/dπnk areas; as tπvets; any spill or leak requiπng more than a couple of paper towels for clean up II Polvmeπc Foam Sheet Charactensttcs

HTPE foams of the present invention are compπsed of specific combinations of monomers which to a large extent control the ultimate properties of the foam. The types of monomers used fall into the following three general categoπes: (1) monomers which help maintain a desirable Tg in the resulting polymer, (2) monomers which help confer "toughness" to the resulting polymer, herein referred to as "toughening monomers", and (3) monomers which have di-, tπ-, tetra-, and higher functionality useful in conferπng crosslinks within the resulting polymer, herein referred to as crosslinkers. These cross nkers are particularly cntical in achieving the desired compressive strength or modulus and/or elasticity which is required for many foam applications. Comonomers which confer strength while lacking sufficient molecular flexibility tend to increase Tg. An example is div yl benzene, a crosslinker wherein higher levels may increase the strength of the polymer while also increasing the Tg. Tg is usually important to the use of any polymer. While in some uses a relatively high Tg may be desired, many uses require a degree of flexibility which requires a lower Tg which m general is more difficult to attain via formulation than a higher Tg. Also, with HIPE foams, the dewateπng process can be significantly complicated m the event of a very high Tg foam (> 100°C)

The polymeπc foams of the present invention are relatively open-celled This means the individual cells of the foam are m complete, unobstructed communication with adjoining cells. The cells m such substantially open-celled foam structures have intercellular openings or "windows" connecting one cell to another withm the foam structure.

These substantially open-celled foam structures will generally have a rettculated character with the individual cells being defined by a plurality of mutually connected three dimensionally branched webs. The strands of polymeπc mateπal making up these branched webs can be referred to as "struts " As used herein, a foam mateπal is "open-celled" if at least 80% of the cells in the foam structure that are at least 1 μm m size are m open communicaUon with at least one adjacent cell This may be determined by inspection of an SEM of the foam.

A. Glass Transition Temperature

Typically, an important parameter of the foams of the present invention is the glass transition temperature (Tg). The Tg represents the midpoint of the transition between the glassy and rubbery states of the polymer Foams that have a Tg higher than the temperature of use can be very strong but can also be very πgid and potentially prone to fracture Though the end use of a particular foam is an important factor when determining the desired Tg of the foam, useful are foams having a Tg of less than 70°C, preferred are foams having a Tg of from about -40° to about 50°C, more preferably from about 0° to about 40°C, most preferably from about 10° to about 30°C. The method for determining Tg by Dynamic Mechanical Analysis (DMA) is descπbed m the TEST METHODS section of U.S. Patent No. 5,753,359 (Dyer et al), issued May 19, 1998, incorporated herein by reference

B. Foam Density

Another potentially important property of the foams of the present invention is their density "Foam density" (i.e., in grams of foam per cubic centimeter of foam volume m air) is specified herein on a dry basis, unless otherwise indicated. Any suitable gravimetπc procedure that will provide a determination of mass of solid foam mateπal per unit volume of foam structure can be used to measure foam density. For example, an ASTM gravimetπc procedure descπbed more fully m the TEST METHODS section of U.S. Patent No. 5,387,207 (Dyer et al.), supra, is one method that can be employed for density determination While foams can be made with virtually any density ranging from below that of air to just less than the bulk density of the polymer from which it is made, the foams of the present invention are most useful when they have a dry density m the expanded state of less than about 80 mg/cc, generally between about 75 and about 38 mg/cc, and more generally between about 63 and 48 mg/cc. The exact preference is dependent on the nature of the application under consideranon and may vary within these ranges.

C. Cell Size

Foam cells, and especially cells that are formed by polymeπzmg a monomer-containing oil phase that surrounds relatively monomer-free water-phase droplets, will frequently be substantially spheπcal m shape. The size or "diameter" of such spheπcal cells is a commonly used parameter for characteπz g foams in general. Since cells m a given sample of polymeπc foam will not necessaπly be of approximately the same size, an average cell size, i.e., average cell diameter, will often be specified.

A number of techniques are available for determining the average cell size of foams. The most useful technique, however, for determining cell size m foams involves a simple measurement based on the scanning electron photomicrograph of a foam sample. (See Figure 1)

The cell size measurements given herein are based on the number average cell size of the foam, e.g., as shown m Figure 1. The foams of the present invention will generally have a number average cell size of not more than about 150 μm, more generally from about 50 to 130 μ m, and most generally from about 80 μm to 120 μm. Wherein two layers of foams are used in the article of the present invention, the upper foam layer will have cell sizes preferably between about 50 and 130 μm and the lower foam layer (lower meaning closest to the impermeable back sheet) will have cell sizes preferably between about 15 and 50 μm. The lower foam layer may be m a "thin-until-wet" condition with enough free volume allowed for full expansion of that layer

HI. Waterproof Component

The mats of the present invention also contain a wateφroof component. This wateφroof component is attached to the back side of the polymeπc foam sheet thus creating a liquid impervious barπer on one side of the sheet. Liquid impervious, as used herein, refers a substance which is incapable of being penetrated by liquids, either hydrophihc or hydrophobic. The wateφroof component(s) suitable for use herein are any composition or substance commonly known in the art For example, wateφroof mateπals are descπbed in U.S. Patent 4,609,580 (Rockett et al.), issued September 2, 1986; 4,822,669 (Roga), issued Apπl 18, 1989; and 5,082,707 (Fazio), issued January 21, 1992; all of which are incoφorated herein by reference. The wateφroof component can be coated onto the back side of the polymeπc foam sheet or in sheet form itself where it is attached to the back side of the foam sheet by lamination, by use of an adhesive or other means commonly known m the art. A wateφroof component m sheet form is impervious to liquids and preferably compπses a thin plastic film, although other flexible liquid impervious mateπals may also be used. As used herein, the term "flexible" refers to mateπals which are compliant and will readily conform to the general shape and contours of the polymeπc sheet. The wateφroof sheet may compπse a woven or nonwoven mateπal, polymeπc films such as films of polyethylene, polypropylene, or polyurethane, or composite mateπals such as a film-coated nonwoven mateπal. A suitable wateφroof sheet is a polyethylene film having a thickness of from about 0.012 mm (0.5 mil) to about 0.051 mm (2.0 mils) Exemplary polyethylene films are manufactured by Clopay Coφoration of Cincinnati, Ohio, under the designation PI 8-1401 and by Tredegar Film Products of Terre Haute, Indiana, under the designation XP-39385. Preferred for use herein are polypropylene/ethylenevmyl acetate films, manufactured by Clopay under the designation PI 8- 3161 The wateφroof sheet may be embossed and/or matte finished to provide a more clothlike appearance. The size of the wateφroof sheet is dictated by the shape and size of the polymeπc film sheet and is sized to match the polymeπc film sheet.

The wateφroof sheet is positioned on the back side of the polymeπc foam sheet and is attached to the polymeπc foam sheet in any manner known in the art, such as, for example, the disclosure m U.S. Patent 4,609,580 (Rockett et al.), issued September 2, 1986. Embodiments of the present invention are also envisioned wherein portions of the polymeπc foam sheet are unattached to the wateφroof sheet. The wateφroof sheet can be secured to the polymeπc foam sheet by a uniform conftnuous layer of adhesive, a patterned layer of adhesive, or an array of separate lines, spirals, or spots of adhesive. Adhesives which have been found to be satisfactory are manufactured by H. B. Fuller Company of St. Paul, Minnesota under the designation HL- 1258 or H-2031, and pressure sensitive hot melt adhesives manufactured by Heartland Adhesive under the designation HI 60. The attachment means will preferably compπse an open pattern network of filaments of adhesive as is disclosed m U.S. Patent 4,573,986 (Mmetola, et al.) issued March 4, 1986, and which is incoφorated herein by reference. An exemplary attachment means of an open pattern network of filaments compπses several lines of adhesive filaments swirled into a spiral pattern such as illustrated by the apparatus and method shown m U.S. Patent 3,911,173 (Sprague, Jr.) issued October 7, 1975; U.S. Patent 4,785,996 (Zwieker, et al.) issued November 22, 1978, and U.S. Patent 4,842,666 (Werenicz) issued June 27, 1989. Each of these patents are incoφorated herein by reference Alternatively, the attachment means may compπse heat bonds, pressure bonds, ultrasonic bonds, dynamic mechanical bonds, or any other suitable attachment means or combinations of these attachment means as are known in the art.

A wateφroof component which is coated on the back side of the polymeπc foam sheet can be any wateφroof composition known in the art which is m a form suitable to be coated, sprayed or m any way uniformly applied to a sheet surface. Such compositions include, but are not limited to fluorocarbon polymers such as are employed m Scotchgard brand products available commercially and manufactured by 3M Co. Essentially any polymer treatment that can render the surface but not mtenor hydrophobic will suffice. The wateφroof component can also be or include a non-slip or skid resistant mateπal and/or process applied to all or a portion of the polymeπc foam sheet so that the mat can be used m a wide vaπety of situations including walking or standing on the mat. Non-s p mateπals are known in the art and include the following: urethane, polyurethane, polyether polyurethane, polyester polyurethane, nylon, and Anti Skid manufactured by Ameπcan Home Products. For example, non-shp or non-skid mateπals and/or processes are described more fully m U.S. Patent 4,609,580 (Rockett et al.), issued September 2, 1986; U.S. Patent 4,609,580 (Rockett et al.), issued September 2, 1986; and 5,500,267 (Canning), issued March 19, 1996; U.S. Patent No. 5,662,758 (Hamilton et al.) issued September 2, 1997; and U.S. patent application Seπal No. 08/744,850 (Hamilton et al.) filed November 8, 1996; all of which are incoφorated herein by reference.

IV. Optional Components

A. Liquid Pervious Sheet

The mats of the present invention can optionally include at least one liquid pervious sheet which is attached to the front side of the polymeπc foam sheet. The term liquid pervious, as used herein, refers to the ability of a substance to permit liquids, either hydrophihc or hydrophobic, to penetrate readily through its thickness. Suitable liquid pervious sheet may be manufactured from a wide range of mateπals such as woven and nonwoven mateπals (e.g., a nonwoven web of fibers), including apertured nonwovens; polymeπc mateπals such as apertured formed thermoplastic films, apertured plastic films, and hydroformed thermoplastic films; porous foams; open-celled foams; reticulated thermoplastic films; and thermoplastic scπms. Liquid pervious sheets can compπse any mateπal such as polyester, polyolefin, rayon, and the like that is substantially porous and permits liquids to readily pass there through and into the underlying polymeπc foam sheet. Suitable woven and nonwoven mateπals can be compπsed of natural fibers (e.g., wood or cotton fibers), synthetic fibers (e.g., polymeπc fibers such as polyester, polypropylene, or polyethylene fibers) or from a combination of natural and synthetic fibers. When the liquid pervious sheet(s) compπses a nonwoven web, the web may be manufactured by a wide number of known techniques. For example, the web may be spunbonded, spunlace carded, wet-laid, melt-blown, hydroentangled, hydroformed, hydroapertured, combinations of the above, or the like.

The liquid pervious sheet(s) is positioned on the front side of the polymeπc foam sheet and is preferably joined completely with the polymeπc foam sheet or joined with a portion of the wateφroof component sheet m any manner known in the art which will not adversely effect the absorbency capabilities of the polymeπc foam sheet. For example, the edges of the liquid pervious sheet(s) can be sealed to the edges of the backsheet using thermal bonded adhesive. Alternatively, the liquid impervious sheet(s) can be attached to the polymeπc foam sheet usmg adhesive and a technique such as spotbondmg. B Other Optional Components

Vaπous other optional components can be utilized herein to alter the tactile feel, appearance, and/or absoφtion properties of the mats. The polymeπc foam sheet, wateφroof sheet and liquid pervious sheet (if present) can be patterned or pπnted with designs. Other components potentially useful herein include colors, odor absorbents such as activated charcoal and cyclodextπn, perfumes, antibacteπals, antimicrobials, and the like can be added. Other items can also be added to expand functtonality in use. For example, an elastic or Velcro type band can be added as an aid for secuπng the mat in place when used over the headrest on the seat of a car.

Any additional component which aids m the functionality in using the mat but does not interfere with its absorbent capacity is suitable for use herein.

V. Preparation of Polymeπc Foams

A. In General Polymeπc foams of the present invention are prepared by polymeπzation of HJPEs.

The relative amounts of the water and oil phases used to form the HJPEs determine the density of the resulting foam. Density is, among many other parameters, cπtical to the mechanical and performance properties of the resulting polymeπc foams. The ratio of water to oil in the emulsion can also influence the cell size and dimensions of the struts that form the foam. The emulsions used to prepare the HIPE foams will generally have a volume to weight ratio of water phase to oil phase of at least about 12: 1, preferably of at least about 13: 1. Typically the volume to weight ratio will be from about 13: 1 to about 25: 1, more typically from about 15:1 to about 20:1. The process for obtaining these polymeπc foams compπses the steps of.

(A) forming a water-in-oil emulsion from-

(1) an oil phase compπsing:

(a) from about 85% to about 98%, by weight of the oil phase, of a monomer component compπsing

(l) from about 45% to about 70%, by weight of the monomer component, of a substantially water-msoluble, monofunctional monomer capable of forming a homopolymer having a Tg of about

25°C or less; (π) from about 25% to about 45%, by weight of the monomer component, by weight of a substantially water-msoluble, monofunctional comonomer capable of imparting toughness about equivalent to that provided by styrene;

(in) from about 3% to about 25%, by weight of the monomer component, of a first substantially water-msoluble, polyfunctional crosslinking agent selected from the group consisting of div yl benzene and analogs thereof; and

(iv) from about 0% to about 15%, by weight of the monomer component, of a second substantially water-msoluble, polyfunctional crosslinking agent selected from the group consisting of diacrylates and dimethacrylates of diols and analogs thereof; and (v) wherein the weight ratio of the monofunctional comonomer capable of imparting toughness (n) to the sum of the first and second polyfunctional crosslinking agents (in + iv) is at least about 1:1; (b) from about 2% to about 15%, by weight of the oil phase, of an emulsifier component which is soluble in the oil phase and which is suitable for forming a stable water-m-oil emulsion;

(2) an aqueous phase compπsing from about 0.1% to about 20%, by weight of the aqueous phase, of a water-soluble electrolyte; (3) a volume to weight ratio of aqueous phase to oil phase of at least about 12: 1; and

(B) polymeπz g the monomer component m the oil phase of the water-m-oil emulsion to form the polymeπc foam.

The term "monofunctionar, as used herein, refers to having one polymeπzable moiety. The term "polyfunctional", as used herein, refers to having more than one polymeπzable moiety. The polymeπc foam mateπal can be subsequently iteratively dewatered and washed to provide a dry, hydrophobic foam. The foam may be rendered hydrophihc by appropπate surface treatment with any of a number of hydrophihzmg agents, including calcium chloπde and similar salts, residual emulsifiers used for stabilizing the HJPE, and other wetting agents well known to those skilled m the art. Hydrophihzmg treatments are descπbed m. e.g., U.S. Patent No. 5,387,207 (Dyer et al.), issued February 7, 1995 (see especially column 22 to column 24), which is incoφorated herein by reference.

These foams may then be shaped mto sheets. These sheets may optionally be compressed, e.g. continuously through pressure nips, mto a thm state and wound mto rolls. Compressible sheets can retain their relatively thm compressed state until unwound, applied as desired, and either heated above their activation temperature (usually about the Tg of the polymer) or allowed to stand for a relatively long peπod of time, e.g. several weeks or months, depending on the ambient temperature, as descπbed m U.S. Patent No. 5,770,634 (Dyer et al.) issued June 23, 1998, mcoφorated herein by reference. Foams are defined as "thin-until-wet" when the foam is compressed to 33% of its oπginal expanded thickness or less and is thereafter maintained without artificial restraint on its surface, the foam will reexpand by no more than 50% after 21 days at 22°C. The method for measuπng this is descπbed m U.S. Patent No. 5,770,634, (DesMarais et al.), issued June 23, 1998, incoφorated herein by reference.

1. Oil Phase Components The continuous oil phase of the HLPE compπses comonomers that are polymeπzed to form the solid foam structure. This monomer component is preferably formulated to be capable of forming a copolymer having a Tg of less than 70°C, generally from about -40° to about 50°C, more generally from about 0° to about 40°C, and most generally from about 10° to about 30°C.

The monomer component of the oil phase may typically compπse Tg loweπng monofunctional monomers, monomers which impart toughness, at least one polyfunctional crosslinking agent, at least one emulsifier. In addition the oil phase may contain additional optional components. Optional oil phase components include antioxidants, plasticizers, filler particles, flame retardants, colorants (dyes or pigments), fluorescent agents, chelants, opacify g agents, and chain transfer agents. The monomer components are descπbed in detail below. The selection of particular types and amounts of monofunctional monomer(s) and comonomer(s) and polyfunctional cross-linking agent(s) can be important to the realization of HLPE foams having the desired combination of structure, and mechanical properties which render such mateπals suitable for use in the invention herein. a. Tg Loweπng Monofunctional Monomers

One component of the oil phase compπses at least one monofunctional comonomer whose atactic amoφhous homopolymer has a Tg of about 40°C or lower (see Brandup. J..

Immergut, E.H. "Polymer Handbook", 2nd Ed., Wiley-Interscience, New York, NY. 1975. JJJ- 139.), described hereinafter as a "Tg loweπng monomer" These monomers tend to impart rubber-like properties to the resulting polymeric foam structure.

Other Tg lowering monomers suitable for use herein are disclosed in U.S. patent

5,770,634 (DesMarais et al.), supra, especially including C4-C12 alkyl styrenes such as p-n- octylstyrene, isoprene, butadiene. 1 ,3.7-octatπene, and piperylene. These monofunctional monomer(s) will generally compπse 45 to about 70%, more preferably from about 20 to about

60%, by weight of the monomer component. b. Comonomers Imparting Toughness.

The monomer component utilized in the oil phase of the HJPEs may also compπse one or more monofunctional comonomers capable of imparting toughness about equivalent to that provided by styrene to the resulting polymeπc foam structure. Tougher foams exhibit the ability to deform substantially without failure. These monofunctional comonomer types can include styrene-based comonomers (e.g., styrene and ethyl styrene) or other monomer types such as methyl methacrylate where the related homopolymer is well known as exemplifying toughness. The preferred monofunctional comonomers of this type are styrene-based monomers including styrene and ethyl styrene. The monofunctional "toughening" comonomer will normally compπse from about 25 to about 45%, preferably from about 30% to about 40%, most preferably about 35% by weight of the monomer component. In certain cases, the "toughening" comonomer can also impart the desired rubber-like properties to the resultant polymer. For such comonomers, the amount that can be included m the monomer component will be that of the typical monomer and comonomer combined. An example is 4-octylstyrene. c. Polyfunctional Crosslinking Agent

The monomer component contains at least one polyfunctional crosslinking agent. As with the monofunctional monomers and comonomers, selection of the particular type and amount of crosslinking agent(s) is important to the realization of polymeπc foams having the desired combination of structural and mechanical properties.

The polyfunctional crosslinking agent can be selected from a wide vaπety of monomers containing two or more activated v yl groups, such as divmylbenzenes and analogs thereof. Analogs of divmylbenzenes useful herein include, but are not limited to, tπvmyl benzenes, divmyltoluenes, div ylxylenes, divmylnaphthalenes divmylalkylbenzenes, divmylphenanthrenes, divmylbiphenyls, divmyldiphenylmethanes, div ylbenzyls, divinylphenylethers, div yldiphenylsulfides. divinylfurans, divmylsulfide, divmylsulfone, and mixtures thereof. Divmylbenzene is typically available commercially as a mixture with ethyl styrene in proportions of about 55.45 These proportions can be modified so as to enπch the oil phase with one or the other component. To provide for a low Tg, it is advantageous to enπch the mixture with the ethyl styrene component while simultaneously reducing the amount of styrene m the monomer blend The cross-linking agent can generally be included in the oil phase of the HIPE m an amount of from about 3 to about 25%, more preferably from about 4 to about 20%, most preferably from about 5% to about 15%, by weight of the monomer component (on a 100% basis).

The crosslinking agent can also be selected from polyfunctional acrylates or methacrylates such as those disclosed m m U.S. Patent No. 5,770,634 (DesMarais et al.), supra. This second cross-linking agent can generally be included m the oil phase of the HIPE in an amount of from 0 to about 15% by weight of the monomer component.

To achieve the toughness and durability required for the current invention, the ratio of toughening monomer to crosshnker is preferred to be at least about 1 :1, preferably about 2:1, and most preferably at least about 4: 1 d. Emulsifiers Another essential component of the oil phase of the HIPE is an emulsifier component.

Suitable emulsifiers are well known to those skilled in the art Particularly preferred emulsifiers include Span 20™, Span 40™, Span 60™, and Span 80™ These are nominally esters of sorbitan deπved from lauπc, myπstic, steaπc, and oleic acids, respectively. In actuality, these contain significant portions of the di- and tπ substituted esters as well as undesired isosorbide esters, polyol components, and other compounds produced duπng the manufactuπng process. It may be preferred to remove especially the isosorbide fraction as much as possible, for example, by distillation. Other preferred emulsifiers mclude the diglycerol esters deπved from monooleate, monomyπstate, monopalmitate, and monoisostearate acids. A preferred coemulsifier is ditallowdimethyl ammonium methyl sulfate and its homologs. Other preferred emulsifiers and coemulsifiers are descπbed in U.S. Patent No 5,650,222 (DesMarais et al.) issued July 22, 1997, incoφorated herein by reference. Mixtures of these emulsifiers are also particularly useful

An optional secondary emulsιfier(s) may be included m the emulsifier component, typically at a weight ratio of pπmary to secondary emulsifier of from about 50: 1 to about 1:4, preferably from about 30.1 to about 2.1. As is indicated, those skilled m the art will recognize that any suitable emulsιfier(s) can be used m the processes for making the foams of the present invention.

The oil phase used to form the HJPEs compπses from about 85 to about 98% by weight monomer component and from about 2 to about 15% by weight emulsifier component. Preferably, the oil phase will compπse from about 90 to about 97% by weight monomer component and from about 3 to about 10%> by weight emulsifier component. The oil phase also can contain other optional components. One such optional component is an oil soluble polymeπzation initiator of the general type well known to those skilled in the art, such as descπbed m U.S. Patent No. 5,290,820 (Bass et al.), issued March 1, 1994, which is incoφorated by reference and WO 97/44368 (Willkomm and Hinze) filed May 23, 1996, which is incoφorated herein by reference. e Optional Components

The oil phase may contain optional components. Such optional components include antioxidants, particularly of the type classified as a Hindered Amine Light Stabilizer (HALS), or a Hindered Phenolic Stabilizer (HPS). Such antioxidants may be applied duπng any convenient step in the processing. Another optional component is a plasticizer such as dioctyl azelate, dioctyl sebacate or dioctyl adipate.

Yet another of the optional ingredients are filler particles which may toughen the polymer and/or increase its thermal insulating properties. Example filler particules include aluminum, titanium dioxide, carbon black (added as very fine, insoluble particles), graphite, calcium carbonate, talc, insoluble, crosshnked flame retardant polymers, and the like. Other optional components include colorants (dyes or pigments), perfumes, chelants such as Zeolites, fluorescent agents, opacifymg agents, chain transfer agents, and the like. Such additives are typically added at fairly low levels when present (e.g., less than 5%) and need not be soluble in the oil phase but may be suspended by agitation therein.

2. Water Phase Components

The discontinuous water internal phase of the HLPE is generally an aqueous solution containing one or more dissolved components. One essential dissolved component of the water phase is a water-soluble electrolyte The dissolved electrolyte minimizes the tendency of monomers, comonomers, and crosslmkers that are pπmaπly oil soluble to also dissolve in the water phase This, in rum, is believed to minimize the extent to which polymeπc mateπal fills the cell windows at the oil/water interfaces formed by the water phase droplets duπng polymeπzation. Thus, the presence of electrolyte and the resulting ionic strength of the water phase is believed to determine whether and to what degree the resulting preferred polymeπc foams can be open-celled.

Any electrolyte capable of imparting ionic strength to the water phase can be used. Preferred electrolytes are mono-, di-, or tπvalent inorganic salts such as the water-soluble halides, e.g., chloπdes, nitrates and sulfates of alkali metals and alkaline earth metals. Examples include sodium chloπde, calcium chloπde, sodium sulfate and magnesium sulfate. Calcium chloπde is the most preferred for use prepaπng the HJPEs Generally the electrolyte will be utilized m the water phase of the HJPEs m a concentration m the range of from about 0.1 to about 20%, by weight of the water phase. More preferably, the electrolyte will compπse from about 1 to about 10%, by weight of the water phase.

The HJPEs will also typically contain an effective amount of a polymeπzation initiator. Such an initiator component is generally added to the water phase of the HJPEs and can be any conventional water-soluble free radical initiator. These mclude peroxygen compounds such as sodium, potassium and ammonium persulfates, hydrogen peroxide, sodium peracetate, sodium percarbonate and the like Conventional redox initiator systems can also be used. Such systems are formed by combining the foregoing peroxygen compounds with reducmg agents such as sodium bisulfite, L-ascorbic acid or ferrous salts.

The initiator can be present at up to about 20 mole percent based on the total moles of polymeπzable monomers present m the oil phase. More preferably, the initiator is present m an amount of from about 0.001 to about 10 mole percent based on the total moles of polymeπzable monomers m the oil phase.

3 Hydrophihzmg Surfactants and Hvdratable Salts

The polymer forming the HLPE foam structure will preferably be substantially free of polar functional groups. This means the polymeπc foam will be relatively hydrophobic in character Removal of the residual emulsifier and/or salt following polymeπzation can be effected as needed by any means including those descπbed m U.S. Patent 5,633,291. Alternatively, the foam may be washed with an aqueous solution of sodium bicarbonate, which converts residual calcium chloπde to the insoluble calcium bicarbonate, which generally greatly reduces the water affinity of the foam. B Processing Conditions for Obtaining HLPE Foams

Foam preparation typically involves the steps of: 1) forming a stable high internal phase emulsion (HJPE), 2) polymeπzing/cuπng this stable emulsion under conditions suitable for forming a solid polymeπc foam structure; 3) optionally washing the solid polymeπc foam structure to remove the oπgmal residual water phase, emulsifier, and salts from the polymeπc foam structure; 4) thereafter dewateπng this polymeπc foam structure; and 5) optionally hydrophihzmg the foam.

C Formation of HLPE The following illustrates a method of preparation of the HJPE foams for use herein.

1. Emulsion Preparation

Anhydrous calcium chloπde (36.32 kg) and potassium persulfate (189 g) are dissolved m 378 L of water. This provides the water phase stream to be used m a continuous process for forming the emulsion. The oil phase is prepared by mixing the monomers chosen the desired proportions, as noted m Table 1 infra.

Separate streams of the oil phase (25°C) and water phase (30°-90°C) are fed to a dynamic mixing apparatus at a combined rate of about 9.1 kg per minute. Thorough mixing of the combined streams in the dynamic mixing apparatus is achieved by means of a pm impeller. The pm impeller compπses a cyhndπcal shaft of about 36.8 cm in length with a diameter of about 2.5 cm. The shaft holds 6 rows of pms, 3 rows having 33 pins and 3 rows having 32 pms, each having a diameter of 0.5 cm extending outwardly from the central axis of the shaft to a length of 2.5 cm The pm impeller is mounted in a cylmdπcal sleeve which forms the dynamic mixing apparatus, and the pins have a clearance of 1.5 mm from the walls of the cyhndπcal sleeve.

A minor portion of the effluent exiting the dynamic mixing apparatus is withdrawn and enters a recirculation zone (see PCT U.S. 96/00082 published 18 July 96 and EPO 96/905110.1 filed 1 1 January 96) The Waukesha pump in the recirculation zone returns the minor portion to the entry point of the oil and water phase flow streams to the dynamic mixing zone. The combined mixing and recirculation apparatus set-up is filled with oil phase and water phase at a ratio of 4 parts water to 1 part oil. The dynamic mixing apparatus is vented to allow air to escape while filling the apparatus completely. The flow rates duπng filling are 7.6 g/sec oil phase and 30.3 cc/sec water phase. These flow rates are modified as the emulsion is formed to achieve the water-to-oil ratio desired.

Once the apparatus set-up is filled the vent is closed. Agitation is then begun in the dynamic mixer, with the impeller turning at the desired rate (e.g., 300 RPM) and recirculation is begun at a rate of about 30 cc/sec. The flow rate of the water phase is then steadily increased to a rate of 65 cc/sec over a time peπod of about 1 mm., and the oil phase flow rate is reduced to 5 g/sec over a time peπod of about 3 mm., or as needed to obtain the water:oιl ratio desired. The recirculation rate is steadily increased to about 150 cc/sec duπng the latter time peπod. The back pressure created by the dynamic mixer and static mixing zone (TAH Industπes Model Number 101-212) at this point is about 1 PSI (7 kPa), which represents the total back pressure of the system. The Waukesha pump speed is then steadily decreased to a yield a recirculation rate of about 75 cc/sec. 2 Polymenzation of Emulsion

The HJPE flowing from the static mixer at this point is collected in a round polyethylene tub, 102 cm in diameter and 31.8 cm high, with removable sides, much like a spπngform pan used in cooking cakes. A pipe-like polyethylene insert 31.8 cm in diameter at its base is firmly affixed to the center of the base and is 31.8 cm high. The HTPE-contaming tubs are kept m a room maintained at 65°C for about 18 hours to effect polymeπzation and form the foam.

3 Foam Washing and Dewateπng

The cured polymeπc foam is removed from the cuπng tubs. The foam at this point has residual water phase (containing dissolved emulsifiers, electrolyte, initiator residues, and initiator) about 12-30 times (12-30X) the weight of polymeπzed monomers. The foam is sliced with a shaφ reciprocatmg saw blade into sheets which are 1-5 mm m thickness. These sheets are then subjected to compression m a seπes of 2 porous nip rolls equipped with vacuum which gradually reduce the residual water phase content of the foam to about 6 times (6X) the weight of the polymeπzed mateπal. At this point, the sheets are then resaturated with an aqueous solution of 1% Pegosperse 200ML and 0.5% CaCl2 solution at 60°C and squeezed m a seπes of 3 porous nip rolls equipped with vacuum to a water phase content of about 2X. The CaCl2 content of the foam is between about 0.5 and 2%.

The foam is then dπed m heating tunnel to reduce the moisture content to about 9% to about 17 % by weight of polymeπzed mateπal At this point, the foam sheets are very flexible.

The following Examples further illustrate the mats of the present invention, but are not intended to be limiting thereof.

EXAMPLE I Table 1 lists the compositions of five polymeπc foams according to the present invention, and one conventional HJPE polymeπc foam that was used as the reference mateπal. TABLE 1.

All of the foams 1-5 of Example I are significantly more durable and resistant to abrasion relative to the reference foam.

EXAMPLE π

The foam from Table 1 Number 1 is cut to a thickness of 2 mm and treated with Pegosperse 200ML as descπbed hereinabove and dπed. Laminate together 1 ml thick polypropylene/ethylenev yl acetate ("PP/EVA") (Clopay PI 8-3161) and the following double side adhesive film: 1 ml thick Heartland HI 60 full coat/0.5 ml thick polyethylene terephthalate/0.7 Heartland HI 60 pattern coat. Cut the polymeπc foam mto sheets. Cut the PP/EVA/adhesive film laminate into sheets.. Laminate together the foam and the PP/ENA/adhesive film laminate. Heat the structure to 140°F for 10 minutes to allow adhesive to flow and increase bond strength. Cut the structures with a rule die according to the desired sizes of the mats to be formed, e.g., 4" x 4", 11" x 11", 12" x 12", 24" x 36", 15" x 19", 36" x 60", etc. Seam together with 3M fabπc tape or 3M medical paper tape large mats with widths of greater than 15". Screen print the top surface of the mat with a pattern for aesthetic reasons (and to identify it as the surface to be exposed). (The pattern may include wπtten instructions, for example The pattern may also mclude puzzles, tic-tac-toe diagrams, connect-the-dots drawings, and the like, to facilitate use m restaurants and/or in nomes with smaller children, for example, for the puφose of providing a protective place mat beneath plates or bowls m which a meal is served ) The mat is then ready for use in any of the places and for any of the functions described in more detail hereinabove

EXAMPLE III. A mat similar to that descnbed m Example II supra is cut to the shape of the tray m the door of a refrigerator and placed therein. On top of this mat is placed, for example, a gallon jug of milk or orange juice The mat absorbs condensate and leakage from the jugs and protects the tray surface of the refrigerator Similarly, the mat may be cut to fit as needed, refrigerator compartments, shelves, cubbyholes, and the like. When the mat becomes sufficiently fouled with exudate from foods and beverages, it can be removed and replaced.

EXAMPLE IV

A large mat similar to that in Example U supra is placed on the ground around any of the following commercial operations, operating rooms duπng surgery to trap blood and other fluids which may otherwise cause slipping, in doctors offices in examination rooms on floors and on examining beds; on the floor of auto repair garages, to collect gasoline and diesel fuel, transmission fluid, motor oil, differential fluid, engine coolant, and the like to prevent slippage and prevent runoff of pollutants into the environment, outside showers at health clubs and schools to prevent tracking of water around the facility; in mdustπal facilities to scavenge dirt, dust, oil, debπs, water, and the like and maintain hygiene and protect against slippery areas; on ships around mechanical equipment, for example, on aircraft earners on the hangar deck where aircraft servicing can lead to fuel spills: in restaurants on floors and food preparation areas, for example to collect spattered grease and oils and food exudates. The mat protects the ground underneath it from unwanted liquids which may cause slippery surfaces, accidents, and unsanitary conditions.

EXAMPLE V. Mats similar to those descπbed in Example JJ supra are placed around homes and offices, for example, on the floors in front of exits to collect mud, dirt, and the like; around locations frequented by pets to collect cat litter, pet hair, pet food, wateπng bowls, and the like; on food preparation areas to collect fluids expressed, for example, duπng meat thawing and/or microwave cooking, which can cross-contaminate other foods and lead to messes; on baby changing tables; at the bottom of trash cans; around bath room sinks, showers, commodes, around laundry areas, on furniture; on top of the mattress pad to serve as absorbent layer for incontinent sleepers including infants, mside shoes and boots. The mats protect the surfaces underneath them from unwanted liquids and or moisture which may cause slippery surfaces, soiled surfaces, unpleasant odors, accidents, and unsanitary conditions.

EXAMPLE VI.

The formulation descπbed in Example I number 5 is modified to replace 2-ethylhexyl acrylate with 2,3-dιbromoacrylate to form a flame retardant exemplification of the foam layer to be used in any of the above applications. The washing treatment for such a mateπal may include alternate salts such as are descπbed in copendmg application U.S. Seπal No. 09/118,613 (Dyer) filed July 17, 1998

EXAMPLE Vπ. A mat similar to that in Example JJ is prepared using two different foam layers. The upper layer compπses a foam which is prepared from the composition descπbed m Example I number 5 prepared using a pm mixer impeller speed of 300 RPM to produce relatively large cells in the resulting foam. This is placed above a second layer prepared from the composition descπbed m Example I number 2 which is prepared using a pm mixer impeller speed of 1500 RPM to produce relatively smaller cells in the resulting foam. This lower foam layer is then secured to the impermeable layer of polyethylene sheeting. This provides for a mat which will acquire fluid rapidly into the upper layer and which will then significantly partition into the lower layer as long as it has unfilled capacity, thus leaving the upper layer relatively dry to the touch.

EXAMPLE VJJJ. A mat is prepared from an oil phase compπsing 50% isoprene, 20% styrene, 15% 1,6- hexanedioldiacrylate, and 15% methyl methacrylate using 3% additional diglycerol monooleate (DGMO) and an aqueous phase compπsing 4% calcium chloπde and 0.15% potassium persulfate. The emulsion is formed as in previous examples but at 25°C and collected in a tub capable of withstanding internal pressuπzation. The tub is pressuπzed using nitrogen to a pressure of 2 atmospheres and placed in a 65°C oven for 2 days. The resulting foam is processed as usual. Duπng the processmg, the foam is washed with an aqueous solution adjusted to pH 4.5 and containing 0.5% Pegosperse 200ML, 0^*5% calcium chloπde, and 0.1% Chimassorb 944 (a product of Ciba Specialty Chemicals). The foam is dewatered and is dπed conventionally. The resulting foam sheet is substantially biodegradable while also being tough and flexible. In yet another example, the same formulation is modified to include chloroprene m place of isoprene to further confer fire retardancv.

Claims

WHAT IS CLAIMED IS :

1 A flexible mat tor absorbing hquids tor use on floors and other suπaces. the mat comprising a) a waterproof component. b) a polymeπc toam sheet haung a tront side and a back side w herein the wateφroot component is attached to the back side such that the back side is liquid impervious, and the polymeπc foam sheet comprises a polymeπzed water-m-oil emulsion hav ing

1 ) an oil phase comprising' a) from about 85 to about 98% by weight of a monomer component, said monomer component compπsing.

I) from about 45% to about 70%, by weight of the monomer component, of a substantially water-insoluble, monofunctional monomer capable of forming a homopolymer having a Tg of about 25°C or less; u) from about 25% to about 45%, by weight of the monomer component, of a substantially water-msoluble, monofunctional comonomer capable of imparting toughness about equivalent to that provided by styrene; in) from about 3% to about 25%. by weight of the monomer component, of a first substantially water-msoluble, polyfunctional crosslinking agent selected from the group consisting of div ylbenzenes, tπvinylbenzenes, divinyltoluenes, divinylxylenes, divinylnaphthalenes divmylalkylbenzenes, divmylphenanthrenes, divmylbiphenyls, divinyldiphenylmethanes, divinylbenzyls, divinylphenylethers, divmyldiphenylsulfides, divinylfurans, divinylsulfide. div ylsulfone, and mixtures thereof; and iv) from 0 to about 15%, by weight of the monomer component, of a second substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of polyfunctional acrylates, methacrylates, acrylamides. methacrylamides, and mixtures thereof; v) wherein the weight ratio of the monofunctional comonomer capable of imparting toughness (n) to the sum of the first and second polyfunctional crosslinking agents (in + iv) is at least about 1 1, b) from about 2% to about 15%, by weight of the oil phase, of an emulsifier component which is soluble in the oil phase and which is suitable for forming a stable water-m-oil emulsion; and 2) a water phase comprising from about 0.1% to about 20% bv w eight of a water- soluble electrolyte, and

3 ) a volume to weight ratio of water phase to oil phase of at least aoout 12.1.

2 The polymeric foam sheet of Claim 1 wherein the weight ratio of the monofunctional comonomer capable of imparting toughness ( n) to the sum of the first and second polyfunctional crosslinking agents (in - iv) is at least about 2: 1

3 The polymeric foam sheet of Claim 1 wherein the weight ratio of the monofunctional comonomer capable of imparting toughness (n) to the sum of the first and second polyfunctional crosslinking agents (in -<^■ iv) is at least about 3: 1.

4 The polymeπc foam sheet of Claim 1 wherein the weight ratio of the monofunctional comonomer capable of imparting toughness (n) to the sum of the first and second polyfunctional crosslinking agents (in ^•*^■ iv) is at least about 5: 1.

5. The polymeπc foam sheet of Claim 1 wherein the oil phase of the emulsion compπses from about 30% to about 40% of the monofunctional comonomer capable of imparting toughness about equivalent to that provided by styrene.

6. The mat of Claim 1 wherein the wateφroof component is a wateφroof composition which is coated on the back side of the polymeπc foam sheet.

7. The mat of Claim 1 wherein the wateφroof component is in the form of a wateφroof sheet which is attached to the back side of the polymeπc foam sheet.

8. The mat of Claim 7 wherein the polymeπc foam sheet has a thickness of from about 0.5 mm to about 5 mm.

9. The mat of Claim 8 wherein the mat has a size selected from the group consisting of 5" x 5", 8" x 10", 11" x 11", 15" x 19", 24" x 36". and 36" x 60".

10. The mat of Claim 8 wherein the wateφroof component further compπses a skid resistant mateπal.

1 1 The mat of Claim 9 used as a floor mat to absorb hydrophihc liquids

12 The mat of Claim 9 used on kitchen surfaces to absorb

liquids

13 The mat of Claim 9 used in a garage to absorb hydrophobic liquids.

14. A flexible mat for absorbing liquids for use on floors and other surfaces, the mat compπsing: a) a wateφroof component; b) at least one liquid pervious sheet; c) a polymeπc foam sheet having a front side and a back side wherein the wateφroof component is attached to the back side such that the back side is liquid impervious, and the polymeπc foam sheet compπses a polymeπzed water-in-oil emulsion having:

1 ) an oil phase compπsing: a) from about 85 to about 98% by weight of a monomer component, said monomer component compπsing: i) from about 45% to about 70%, by weight of the monomer component, of a substantially water-msoluble, monofunctional monomer capable of forming a homopolymer having a Tg of about 25°C or less; n) from about 25% to about 45%, by weight of the monomer component, of a substantially water-insoluble, monofunctional comonomer capable of imparting toughness about equivalent to that provided by styrene; iii) from about 3% to about 25%, by weight of the monomer component, of a first substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of divmylbenzenes, tπvinylbenzenes, divinyltoluenes, divmylxylenes, div ylnaphthalenes div ylalkylbenzcnes, divinylphenanthrenes, divinylbiphenyls, divinyldiphenylmethanes, divmylbenzyls, div ylphenylethers, div yldiphenylsulfides, divinylfurans, divinylsulfide, div ylsulfone, and mixtures thereof; and iv) from 0 to about 15%, by weight of the monomer component, of a second substantially water-msoluble, polyfunctional crosslinking agent selected from the group consisting of polyfunctional acrylates, methacrylates, acrylamides, methacrylamides, and mixtures thereof; 2"

\ i w herein me w eight ratio of the monotunctional comonomer capable of impaπing toughness ( π ) to the sum ot the first and second polyfunctional crosslinking agents ( in -

) is at least about 1 ^• 1. b) trom about 2% to about 15%, by weight of the oil phase, of an emulsifier component which is soluble in the oil phase and which is suitable for forming a stable water-in-oii emulsion, and

2) a water phase comprising from about 0.1% to about 20% by weight of a water- soluble electrolyte: and

15. The polymeπc foam sheet of Claim 14 wherein the weight ratio of the monofunctional comonomer capable of imparting toughness (u) to the sum of the first and second polyfunctional crosslinking agents (in + iv) is at least about 2: 1.

16 The polymeπc foam sheet of Claim 14 wherein the weight ratio of the monofunctional comonomer capable of imparting toughness (n) to the sum of the first and second polyfunctional crosslinking agents (in ^•*^■ iv) is at least about 3: 1.

17 The polymeπc foam sheet of Claim 14 wherein the weight ratio of the monofunctional comonomer capable of imparting toughness (n) to the sum of the first and second polyfunctional crosslinking agents (in + iv) is at least about 5: 1.

18. The polymeπc foam sheet of Claim 14 wherein the oil phase of the emulsion compπses from about 30% to about 40% of the monofunctional comonomer capable of imparting toughness about equivalent to that provided by styrene.

19. The mat of Claim 14 wherein the liquid pervious sheet is attached to the front side of the polymeπc foam sheet and is selected from the group consisting of woven and nonwoven mateπals, natural fibers, synthetic fibers, and combinations thereof.

20. The mat of Claim 19 wherein the wateφroof component is a wateφroof composition which is coated on the back side of the polymeπc foam sheet.

21 The mat of Claim 19 w herein the wateφroof component is in the form of a wateφroof sheet which is attacned to the back side of the polymeric foam sheet

22 The mat of Claim 21 wherein the polymeric foam sheet has a thickness of from about 0 5 mm to about 5 mm

23 The mat of Claim 21 wherein the wateφroof component fuπher comprises a skid resistant material

24 The mat of Claim 23 used as a floor mat to absorb hydrophihc liquids.

25. The mat of Claim 23 used in a garage to absorb hydrophobic liquids.

26 The mat of Claim 23 used as shoe or boot inserts.

27 The mat of Claim 23 wherein the mat has a size selected from the group consisting of 5" x 5". 8" x 10", 1 1" x 1 1", 15" x 19", 24" x 36", and 36" x 60".

28. A method for manufactuπng a flexible mat for absorbing liquids for use on floors and other surfaces, compπsmg the steps of:

(A) creating a polymeπc foam sheet, having a front side and a back side, by forming a water-m-oil emulsion from: ( 1 ) an oil phase comprⁱsing:

(a) from, about 85% to about 98%, by weight of the oil phase, of a monomer component compπsing:

(0 from about 45% to about 70%, by weight of the monomer component, of a substantially water-msoluble, monofunctional monomer capable of forming a homopolymer having a Tg of about 25°C or less; (n) from about 25% to about 45%, by weight of the monomer component, by weight of a substantially water-msoluble, monofunctional comonomer capable of imparting toughness about equivalent to that provided by styrene; ( in) from about 3% to about 25%, by weight of the monomer component, of a first substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of divinyl benzene and analogs thereof; and (iv) from about 0% to about 15%, by weight of the monomer component. of a second substantially water-insoluble, polyfunctional crosslinking agent selected from the group consisting of diacrylates and dimethacrylates of diols and analogs thereof; and v) wherein the weight ratio of the monofunctional comonomer capable of imparting toughness (u) to the sum of the first and second polyfunctional crosslinking agents (iii + iv) is at least about 1 : 1; and (b) from about 2% to about 15%, by weight of the oil phase, of an emulsifier component which is soluble m the oil phase and which is suitable for forming a stable water-in-oil emulsion;

(2) an aqueous phase compπsing from about 0.1% to about 20%, by weight of the aqueous phase, of a water-soluble electrolyte;

(3) a volume to weight ratio of aqueous phase to oil phase of at least about 12: 1; and

(B) polymenzing the monomer component m the oil phase of the water-m-oil emulsion to form the poiymeπc foam sheet; and

(C) attaching a wateφroof component to the back side of the polymeπc foam sheet.

29. The method accordmg to Claim 28 further compnsmg attachmg at least one liquid pervious sheet to the polymeπc foam sheet.