CA2262584A1 - Permeable, liquid flow control material - Google Patents

Abstract

A permeable, liquid flow control material composed of: 1) a permeable sheet having a plurality of individual exposed surfaces, at least a portion of which have a surface energy of less than about 45 dynes/cm; and 2) amphiphilic proteins adsorbed onto at least some individual exposed surfaces to define a gradient distribution of amphiphilic protein coating along at least one dimension of the permeable sheet so that the adsorbed amphiphilic protein coating provides controlled wettability along at least one dimension of the liquid flow control material. Desirably, the liquid flow control material is substantially free of fugitive amphiphilic proteins. The material may be used as a permeable, bodyside cover material for absorbent personal care products.

Description

CA 02262~84 1999-02-02 PERMEABLE, LIQUID FLOW CONTROL MATERIAL

FIELD OF THE INVENTION
This invention relates to permeable materials that are wettable.

BACKGROUND OF THE INVENTION
Sheets of apertured films, woven fabrics and nonwoven r"dlerials are widely used in many types of products such as, for example, personal care products, garments, medical fabrics and the like. Some sheets made from certain inexpensive raw ",alèrisls could have 10 an even wider range of a~p'ic7tions in these products if the sheets could be designed to have enhanced properties or attributes.
For exar"F'e, polyolefins are widely used in the manufacture of sheets of apertured films, woven fabrics, and nonwoven ",alerials. Many types of polyolefin sheets tend to be hydluphobic and relatively inert. That is, the low surface free energy of polyolefins (e.g., polypropylene) and their relatively chemically inert nature render many u"r"odified polyolefins ill-suited for providing attributes other than those based on hydrophobic interactions.
In the past, chemical coalil,gs and/or intemal additives have been added to sheets of ",dlerials to impart desired properties. Many of these coali"gs and/or additives present problems related to cost, effectiveness, durability and/or the environment. These coalings generally provide a uniform wettability or hydrophilicity across one or more dimensions of the sheets of materials. Sheet ",dler.als having sul,~lanlially uniform wettability across their thickness or Z-direction may retain or hold sig"ificanl amounts of liquid in the cover ",dlerial instead of releasing the liquid to an absorbent core. This may be particularly n~,t~ b'e if the liquid is colored or viscous in nature such as, for example, blood or r"enses. Thus, there is still a need for a permeable material having controlled, non-uniforrn wettability so that it can be used to direct the l,~,-srer or flow of liquid through the maLe,ial. There is also a need for a permeable, bodyside cover ",alerial for use in an absorbent per:,onal care product. There is also a need for a perrneable, bodyside cover material for use in an absorbent pe,~onal care product which provides non-unifomm wettability along at least one dimension of the cover maLerial. This need extends to a perrneable, bodyside cover r~alerial (for an absorbent personal care product) coated with a readily available, inexpensive, natural, renewable and non-toxic material that can provide non-uniform wettability to a relatively hydluph~b.~
substrate. Meeting these needs is i,,,pu,lanl since it is both econGr". ~lly and env;,un",enlally desirable to s(lhstitllte relatively complex chemical surface moc3ific~lion of inexpensive (and often recyclable) substrates with inexpensive, readily available natural ",aleria:s.

CA 02262~84 1999-02-02 W O98/09016 PCT~US97/12536 DEFINITIONS
As used herein, the term "amphiphilic protein" refers to prulei"s having both hyd,ophab c regions and hydlophilic regions. For example, ar"ph;philic proteins may be selected from classes of globular and/or random coil pr~jtoins. As another example, amphiphilic pr~tei"s may be milk pr~tei"s. As a further exan,, IB, amphiphilic proteins may indude p,utei.~s such as those found in bovine milk including, but not limited to, various caseins and whey prute~)s.
As used herein, the temm "relatively low surface energy" refers to surface energies (i.e., surface free energies) attributed to materials that are not generally considered to be water 10 wettable. Generally speaking, such materials have a surface energy of less than about 45 dynes per cenli",eler (dynes/cm) as determined in accordance ~vith critical surface tension of wetting techniques described by Bennet, M.K. and Zisman, W.A.; Relation of WettabilitY by Aqueous Solutions to the Surface Constitution of Low Ener~Y Solids: ~. Phys. Chem., pps.
1241-1246, Volume 63 (1959). Many such "l~le,ials have a surface energy ranging from about 29 to about 35 dynes/cm.
As used herein, the term "relatively high surface tension" refers to a level of attractive force in a liquid exerted by the molecules below the surface upon those at the surface/air i"Le,rt,ce, resulting from the high molar concentration of a liquid ~n,par~d to the low molar concent,ation of a gas. Relatively high surface tensions are characteristic of, for example, some aqueous liquids and/or aqueous solutions having little or no added s~"ra~la,)l~ or other agents that reduce the surface tension. Surface tension may be detennined from measu,~",enls of the contact angle of sessile drops using a gon,arneter such as, for example gon:o,",eler model No. 10~00 115 (equipped with videocamera) available from Rame-Hart, Inc., or by Illelllods such as, for example, DuNouy ring methods. Relatively high surface tension for the purposes of the present invention is a surface tension of at least about 45 dynes/cm. Desirably, the surface tension is greater than 45 dynes/cm.
As used herein, the teml "shear stress condilions" refers to cond;'ions under which a shed,i"g stress (force per unit area) is applied to a liquid. As an example, for a given volume of a liquid, increasing the rate at ~,vhich the liquid penet,dles or passes through a relatively pe""e~'9~ sheet such as, for example, a polyolefin nonwoven fibrous web (i.e., by decreasing the residence or exposure time) results in an increased shear stress at the fiber/liquid inle,f3ce. Generally speaking, shear stress applied to the liquid may be transferred or applied to amphiphilic r"ac~umalec~'es that may be present in the liquid. In addilion to shear stress conditions, residence time or dwell time may also need to be suffcient for the 35 amphiphilic n,a~;lulllolecllle to interactwith the surface of a substrate (e.g., permeable sheet).
Residence time may be influenced by the thickness and/or basis weight of a pemmeable CA 02262~84 1999-02-02 W O 98/09016 PCT~US97/12536 sheet. A relatively long residence time may generally indicate little or no shear stresses and a relatively short residence time may generally indicate shear stress conditions. Shear stress conditions may occur in liquid flow having generally laminar or turbulent flow cl ,aracleri:,tics.
As used herein, the teml "adsorbed" refers to a type of adhesion which takes place at the surface of a solid in contact with another medium (e.g., a liquid), resulting in the accumulation or increased concentration of mc'ecl~'es from that medium in the immediate vicinity of the surface.
As used herein, the term "nonwoven web" refers to a web that has a structure of individual fibers or rild"le"l~ which are interlaid, but not in an idenlirl-'~'e repeating manner.
l0 Nonwoven webs have been, in the past, formed by a variety of processes known to those skilled in the art such as, for example, meltblowing, spunbonding, wet-forming and various bonded carded web processes.
As used herein, the term "spunbonded web" refers to a web of small diameter fibers and/or rilalllenls which are formed by extruding a molten themmoplastic material as filaments 15 from a plurality of fine, usuaily circular, capillaries in a spinnerette with the diallleter of the extruded filaments then being rapidly reduced, for example, by non-eductive or eductive fluid-drawing or other well known spunbonding mecl,anis,ns. The production of spunbonded nonwoven webs is illustrated in patents such as Appel, et al., U.S. Patent No. 4,340,563.
As used herein, the temm "meltblown fibers" means fibers formed by extruding a molten 20 thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into a high ve~ocily gas (e.g. air) stream which attenuates the filaments of molten themmoplastic ",dlerial to reduce their ~Jia")eler~, which may be to microfiber did" ,eter.
Thereafter, the meltblown fibers are carried by the high veloci~y gas stream and are deposited on a collecting surface to form a web of randomly dispersed meltblown fibers. The 25 meltblown process is well-known and is described in various patents and publications, including NRL Report 4364, "Manufacture of Super-Fine Organic Fibers" by V.A. Wendt, E.L.
Boone, and C.D. Fluharty; NRL Report 5265, "An Improved Device for the Fo",ldlion of Super-Fine Thel"~opldslic Fibers" by K.D. Lawrence, R.T. Lukas, and J.A. Young; and U.S.
Patent No. 3,849,241, issued November 19, 1974, to Buntin, et al.
As used herein, the temm "microfibers" means small did",eter fibers having an average dia",eler not greater than about 100 microns, for example, having a diameter of from about 0.5 microns to about 50 microns, more specifically microfibers may also have an average diameter of from about 1 micron to about 20 microns. Microfibers having an average dia",eler of about 3 microns or less are cor",nonly referred to as ultra-fine microfibers. A
35 descriplion of an exe~plary process of making ultra-fine microfibers may be found in, for CA 02262~84 l999-02-02 example, U.S. Patent No. 5,213,881, entitled "A Nonwoven Web With Improved Barrier Properties".
As used herein, the term "apertured film-like material" refers to a generally flat or planar layer of material which has been punched, drilled, apertured, ~ 1 ;hed, perforated, ell ,bossed, patterned, crinkled and/or otherwise processed so that it may have relatively gross or visible openings with or without a pattem or texture in the thickness dimension (i.e., Z-direction) of the ,~alerial. Exemplary apertured film-like ~"al~ria:s include, but are not limited to, perf-embossed films, textured apertured films, retiu lloted apertured films, contoured apertured films, film-nonwoven apertured lar"in~les, and expanded plexi-fild" ,enlary films.
0 As used herein, the term "sheet" refers to a material that can be a woven fabric, knit fabric, nonwoven fabric or film-like material (e.g., an apertured film-like material).
As used herein, the tenn "solution" refers to any relatively uniformly dispersed mixture of one or more substances (e.g., solute) in one or more other substances (e.g., solvent).
Generally speaking, the solvent may be a liquid such as, for example, water and/or mixtures of liquids. The solvent may contain additives such as salts, acids, bases, viscosity modifiers, preservatives, disinfectants, anti-microbial agents and the like. The solute may be any material adapted to uniformly disperse in the solvent at the apprupriale level, (e.g., ionic level, ",c'ecl ~ level, co".,.~' particle level or as a suspended solid). For example, a solution may be a unifomlly dispersed mixture of ions, of m~'su~'es, of colloid~l particles, or may even include mechanical suspensions.
As used herein, the temms "permeable" and "pemmeability" refer to the ability of a fluid, such as, for example, a gas to pass through a particular porous r"~lerial. Pemmeability may be expressed in units of volume per unit time per unit area, for example, (cubic feet per minute) per square foot of ",alerial (e.g., (ft3/minute/ft2)). Permeability may be detemmined utilizing a Frazier Air Permeability Tester available from the Frazier Precision Instrument Company and measured in accoldance with Federal Test Method 5450, Standard No. 191A, except that the sample size was 8" X 8" instead of 7" X 7". Although pemmeability is generally expressed as the ability of air or other gas to pass through a permeable sheet, sufficient levels of gas permeability may correspond to levels of liquid pemleability to enable the prd~lice of the present invention. For exam~'e, a suffcient level of gas permeability may allow an adequate level of liquid to pass through a permeable sheet with or without assi~lance of a driving force such as, for example, an applied vacuum or applied gas pressure. Generally speaking, a pemmeable sheet may have a permeability of at least about 20 cubic feet per minute per square foot (cfm/ft2), as measured for a suL,~lanlially dry sheet priorto prucessi, Ig. It is conle",,~ led that a sheet having a permeability of less than about 20 cfm/ft2, as measured for a substantially dry sheet prior to processi"g, could be used CA 02262~84 1999-02-02 W 0 98/09U16 PCT~US97/12536 su~ressfully in the pr~,lice of the present invention with (or in some cases without) assijLance of a driving force such as, for example, an applied vacuum or applied gas pressure. As an ~-dlll,~ 'E, a permeable sheet may have a pemmeability of from about 25 to over 200 cfm/ft2, as measured for a suL~la~ Itially dry sheet prior to processing. As another exdm,~ 'e, a pemmeable sheet may have a pemmeability of from about 35 to about 150 cfm/ft2, as measured for a substantially dry sheet prior to processing.
As used herein, the temm "superabsorbent" refers to abso,L,enl n,~lerials capable of abso,L ng at least 10 grams of aqueous liquid (e.g. water, saline solution or synthetic urine Item No. K-C 399105 available from PPG Industries) per gram of absorbent material while 10 immersed in the liquid for 4 hours and holding the absorbed liquid while under a con,l.r~ssion force of up to about 1.5 pounds per square inch.
As used herein, the temm "consisting essentially of" does not exclude the presence of add;tional materials which do not sig"ir,canlly affect the desired chal~utarisLics of a given co"~posilion or product. Exe",plaly ~ lerials of this sort would include, without limitation, 15 pigments, antioxidants, stabilizers, surfactants, waxes, flow promoters, partic~ l'atrs or ",dlerials added to enhance prucessAbility of a composition.

SUMMARY OF THE INVENTION
The problems described above are adJ,assed by the present invention which is 20 directed to a pemmeable, liquid flow control ",alerial composed of: 1) a pemmeable sheet having a plurality of individual exposed surfaces, at least a portion of which have a surface energy of less than about 45 dynes/cm; and 2) amphi~,hilic proteins adsorbed onto at least some individual exposed surfaces to define a gradient distribution of amphiphilic protein coating along at least one dimension of the permeable sheet so that the adsorbed amphiphilic 25 protein coating provides cor,Lf~l'e~ wettability along at least one dimension of the liquid flow control material. Desirably, the liquid flow control material is subslantially free of fugitive amphiphilic proteins. That is, the amphiphilic pr~ ins adsorbed to the pe""e :'~'e sheet are substantive to water wash and other aqueous solution washes.
The amphiphilic pr-,tei,1s may be adsorbed onto at least some individual exposed30 surfaces thereby defining a pattemed protein coating on the pemmeable sheet. The coating of amphiphilic prc.te;ns may be ~" ,iro""ly adsorbed onto individual exposed surfaces but in only discrete po~lions of the sheet ",ale,ial.
Generally speaking, the amphiphilic pr~tei. ,s may be selected from the group consi~ling of globular proteins and random coil proteins. The amphiphilic protein-coated sheet desirably 35 has a critical surface tension of wetting greater than about 50 dynes per cenli",ater. For CA 02262~84 1999-02-02 W O 98/09016 PCT~US97/12536 exdmr e the amphiphilic protein-coated sheet may have a critical surface tension of wetting greater than about 60 dynes per centi" ,eler.
In an aspect of the invention the liquid flow control material may have a liquid ~terlLion of less than about 3.5 percent by weight. For example the ",~lerial may have a liquid ,t:te"lion of less than about 2 percent by weight. In another aspect of the invention the liquid flow control material may have a liquid retention of greater than about 3.5 percent by weight when surface or side of the ~alerial having the lower surface tension of wetting is the surface or side which first conld.l~ the liquid. For example the liquid flow control malerial may have a liquid (elenlion of up to about 5 percent by weight and provide a relatively stain-free and/or 10 relatively dry surface when surface or side of the ",alerial having the lower surface tension of wetting is the surface or side which first contacts the liquid.
The liquid flow control ",dLerial may have a gradient distribution of amphiphilic protein coating along at least two dimensions of the permeable sheet. Accordingly the adso~bed amphiphilic protein coating may provide ~nL,~l'ed wettability along at least two dimensions of 15 the pel",~ sheet.
According to the invention the pemmeable sheet may be a matlix of fibrous ",dlerial.
For example the permeable sheet may be selected from nonwoven webs of meltblown fibers, nonwoven webs of continuous spunbond filaments and bonded carded webs. The nonwoven web of meltblown fibers may include one or more secondary ",alerials selectPd 20 from the group consisting of textile fibers wood pulp fibers partic~ s and super-absorbent materials. In an embodiment of the invention at least a portion of the fibrous material is a bi-cGr"ponent material selected from bi-component fibers and bi-co",ponent filaments. In another embodiment the pe~ eable sheet may be an apertured film-like l"dlerial.
Generally speaking the permeable liquid flow control mdleridl may be used in 25 app ~tions where it is desirable to direct the flow pass~ge or distribution of a liquid within or through a permeable ",dtelial. The material may be included in products such as for eAd", ~ o, surgical pads bed pads liquid applicator devices and the like. The ",dl~rial may be used as a liquid intake ",alenal liquid distribution male(ial or liquid lelention ",alerial in the products described above as well as in absorbent personal care products.
According to the invention the permeable liquid flow control ",dlerial may be in the fomm of a pe~ eable bodyside cover ",aLerial for absorbent per~onal care products. Such cover materials may be used in personal care products including but not limited to feminine care products diapers training pants adult incor)linence products and the like.
In an embodiment of the invention the permeable liquid flow control n,dlerial may 35 utilize amphil,hilic mac,o",~ ocl~'es as the l"alerial adsorbed on at least some individual PYposed surfaces of the pemmeable sheet. Such alllphiphilic macromo'ecues may include but CA 02262~84 1999-02-02 W O 98109016 PCT~US97/12536 are not limited to, synthetic polymers such as ionomers with sepa,dled areas of ionicity in an otherwise hydrophobic polymer, multiblock copolymers where every other block is highly charged or polar with the intervening blocks uncharged or nonpolar, protein,fatty acids, glycoprote;. ~s, and other biological macromolecules with separated areas of hydrophilicity and 5 hyd, uphobicity BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a micrograph of an e~emplary protein-coated permeable sheet.
FIG. 2 is a represenldlion of a stained, vacuum extracted, exe",,.lary protein-coated 10 permeable sheet.
FIG. 3 is a representation of exemplary solvent durability of protein coa~illgs on a pemmeable sheet.
FIG. 4 is a representdlion of the effects of soaking an exe",plary protein-coated pemmeable sheet on the fluid surface tension of the soaking solution.
FIGS. 5A and 5B are photographs of an absorbent personal care product and pe""~'o cover ",a~erial.
FIGS. 6A and 6B are photographs of an absorbent personal care product and pe"neable cover ",alerial.
FIGS. 7A and 7B are photographs of an abso, L,eol personal care product and pemmeable cover mdlerial.

DETAILED DESCRIPTION OF THE INVENTION
An exemplary method of applying a protein coating to a substrate is described in U.S.
Patent No. 5,494,744 to Everhart et al., issued on Febnuary 27, 1996, the contenls of which is incc,,,uo,dled by rerer~nce. Such a method may be employed to apply an amphiphilic ",ac,umolecule (e.g., amphiphilic protein) coating to a substrate to manufacture a permeable, liquid flow control material. Such a method may also be used lo manufacture a pemleable, bodyside cover material for absorbent personal care products. Such cover ",dlerials may be used in personal care products including, but not limited to, feminine care products, diapers, training pants, adult incontinence products and the like.
Generally speaking, the method includes the steps of coating individual ~Yposed surfaces of a pemmeable rnalerial (e.g., a matrix of fibrous material or an apertured film-like ",aterial) with amphiphilic macromclecu'es (e.g., amphiphihlic proteins).
The permeable sheet may be unwound from a supply roll or may be fommed by one ormore sheet making processes and passed directly into the coating process. Exemplary sheet-making processes include processes such as m~ i, lg processes, spunbonding CA 02262~84 1999-02-02 W O 98/09016 PCT~US97/12536 processes, bonded-carded web-making processe.s, wet-laying processes, apertured film-forming processes, and the like. The pemmeable sheet may be passed through a pre-treatment station to modify the structure of the sheet. For e,cd",,~'e, the sheet may be calendered with a flat roll, point bonded or pattern bonded roll and/or aperturing roll in order to 5 achieve desired sl,~:nyLI" functional and/ortextural properties. Although it is not necess~ry for the successful deposilion of the amphiphilic n,au,u,no'Ecule (e.g., amphiphilic protein) coating on the pemmeable sheet in the prdctice of the present invention, it is conlemplaled that at least a portion of a surface of the sheet could be modified by various known surface mocliticdlion tec,l",.~ues prior to entering the continuous process of coating 10 individual exposed surfaces of the pemmeable sheet with amphiphilic ,,,ac,ur~ulec~es Exemplary surface modiricdlion techn.~ues include, for example, chemical etching, chemical oxidation, ion bomb~,d",el~t, plasma treatments, flame treatments, heat treatments, and/or corona dis~l ,a, ye treatments.
The pemmeable sheet may be an apertured film-like ,nalerial. For e~.d",r'e, the apertured film-like material may be selected from perf-e",bossed films, textured apertured films, reticulated apertured films, contoured apertured films, flm-nonwoven apertured laminates, and expanded plexi-filamentary films.
Alternatively and/or additionally the permeable sheet may be a matrix of fibrous " ,aterial such as one or more woven fabrics, knit fabrics or nonwoven fabrics. That is, the pemmeable sheet may be either an apertured film-like mdlerial, a matrix of fibrous ",alerial or any suitable co" Ib . ~dlion of the same. If the pemmeable sheet is a nonwoven fabric, it may be a nonwoven fibrous web such as, for example, a bonded carded web, spunbond web, web of meltblown fibers, fibrous batt, fibrous mat and/or multi-ply fibrous web containing the same type of fbrous web or a multi-ply fibrous web containing dirrerenl types of fibrous webs. If the permeable sheet is a web of meltblown fibers, it may include meltblown microfbers. These nonwoven webs may be fommed from ll,em,opl~lic polymers orther",osel polymers. If the nonwoven web is formed from a polyolefin, the polyolefin may be polyethylene, polypropylene, polybutene, ethylene copolymers, propylene copolymers and butene copolymers. The fibers and/or filaments may be fommed from blends that contain various pigments, additives, strengthening agents, flow modifiers and the like. Such fabrics are described in U.S. Patent Nos. 4,041,203, 4,374,888, and 4,753,843, the contents of which are incorporated herein by ~fe~t:nce. Those patents are assigned to the Kimberly-Clark Corporation, the assignee of the present invention.
The permeable sheet may be a nonwoven web that may also be a composite i"alerial35 made of a mixture of two or more dirr~r~nl fibers or a mixture of fibers and partic~ tes Such mixtures may be formed by adding fibers and/or particulates to the gas stream in which CA 02262~84 1999-02-02 W O 98/09016 PCT~US97/12536 meltblown fibers are carried so that an intimate entangled commingling of meltblown fibers and other ~ lerials e.g. wood pulp staple fibers and particu'~tes such as for example activated carbon silica and/or hydrocolloid (hydrogel) particulates commonly referred to as superabsorbent materials occurs prior to collection of the meltblown fibers upon a collecting device to form a coherent web of randomly dispersed meltblown fibers and other ",al~ria s such as ~lis~losed in U.S. Patent Nos. 4 100 324 and 5 350 624 the ~isclos~re of which is hereby incorporated by re~ nce.
If the permeable sheet is a nonwoven web the fibrous ~,aLerial in the nonwoven web may be joined by interfiber bonding to form a coherent web structure. Ir,t~:, r,L er bonding may 1C be produced by entanglement between individual meltblown fibers carded fibers spunbond filaments and/or other fibrous materials. Some fiber entangling is inherent in the meltblown process bonding-carding process and/or spunbond process but may be generated or increased by processes such as for example hydraulic entangling or needlepunching.
Alternatively and/or additionally a bonding agent may be used to increase the desired bonding. If at least a portion of the fibrous material in the pemmeable sheet is cellulosic fibrous material some interFlber bonding may be attributable to pape~ bonding.
The permeable sheet (either before or after processing) may have a basis weight ranging from about 6 gsm to about 400 gsm. For example the pemmeable sheet may have a basis weight ranging from about 12 gsm to about 250 gsm. Desirably the pemmeable sheet may have a basis weight ranging from about 17 gsm to about 102 gsm. It is contemplated that after processing any number of treated pemleable sheets may be joined together or treated permeable sheets may be joined to other ",a~erials to form a consol.d-'~d material that may have a basis weight within the range of 6 gsm to 400 gsm or even greater (e.g. 400 gsm or more).
In order to apply an amphiphilic ~"ac,u",olecule coating the pemmeable sheet passes under a means or device for providing a solution containing alllph;l~hilic n~ac,ulllcleclllos While the solution is typically an aqueous solution it is conle",~.ldLed that non-aqlleous solutions may be used. Such non-aqueous solutions may contain one or more organic solvents. In some cases it is contemplated that the organic solvents might affect the confor~alion of the amphiphilic macromc ecl~'es to enhance adso,~tion.
Generally speaking the a,nphi~)h lic ",acrumc'eo ~PS may be amphiphilic pru~i )s. The aqueous solution of amphiphilic macromolecules (e.g. amphiphilic proteins) should have a relatively high surface tension (i.e. the aqueous solution of amphiphilic ",ac,uri,o ec~ s should have a surface tension of about 45 dynes/cm or greater). The means for providing an aqueous solution containing a",phiphilic n,acru",olecules distributes the ~queous solution su~la,1lially across and onto a first surface of the continuously advancing pemmeable sheet.

CA 02262~84 1999-02-02 W 098tO9016 PCTAUS97/12536 The means or device for depositing the aqueous solution containing amphiphilic mac,urr,n'ec~ ~'es (e.g., amphiphilic proteins) deposits the amphiphilic "~acromolecules at conditions under which a shearing stress is applied to the aqueous solution. A description of such co"dit;ons may be found at, for example, U.S. Patent No. 5,494,744, previously s i"co,,uo,dled by reference.
The liquid depositing device may be composed of at least one liquid distributionelement. For example, multiple liquid distribution ele."enl~ may be arranged in series. The liquid distribution element may be a spillway adapted to produce a stream or shower of the aqueous solution of amphiphilic ",acrol"olecules (e.g., amphiphilic proteins) so that it is under 10 shear stress conditions as it conla.;l~ the permeable sheet. The liquid distribution element may also be one or more nozles and/or orifices which sprays, squirts, ~ets or otherwise conveys the aqueous solution so that it is under shear stress conditions as it contacts the pemmeable sheet. It is contemplated that the liquid distribution element may be col"posed of a reservoir of the aqueous solution of amphiphilic ",ac,u,nolecules (e.g., amphiphilic proteins) 15 designed so that the pel", ~'e sheet passes over either an interior or exterior surface across one or more openings or orifices which provides contact with the aqueous solution of amphiphilic macromo!~u~'e~ (e.g., amphiphilic proteins) under shear stress conditions. It is also conlen,plated that the liquid distribution element may be a reservoir of the aqueous solution into which the permeable sheet passes at a rate of travel through the reservoir such 20 that shear stress conditions are created at the i,lte,race between one or more surfaces of the pemmeable sheet and the aqueous solution.
The liquid distribution element may be composed of a reservoir and a spillway adapted to produce a relatively unifomm distribution of the aqueous solution to produce a layer of liquid on top of the permeable sheet. A vacuum may be applied simultaneously with (and on the 25 surface opposile to) the deposition of the aqueous solution to generate shear stress conditions in the aqueous solution as it passes through the permeable sheet. It is co,llel"plated that arplio~tion of vacuum may be delayed so that it is not simultaneous with the deposition of aqueous solution. Generally speaking, the vacuum level shouid be sufficient to draw the aqueous solution through the permeable sheet under shear stress 30 conditions. As an example, the vacuum level may be greater than about 60 inches of water.
As another exan ,ple, the vacuum level may range from about 60 to about 270 or more inches of water. A desc,i,utiol1 of an exemplary liquid distribution element may be found in U.S.
Patent No. 5,486,381, which is assigned to the assignee of the present appli~lion, the conlenL~ of which are incorporated by reference in their entirety.
As discussed above, the means for applying a vacuum to a second surface of the continuously advancing permeable sheet are located near the liquid deposition element.

CA 02262~84 l999-02-02 Generaliy speaking, the vacuum means may be composed of at least one vacuum element.
Multiple vacuum elements may be arranged in series. The vacuum element may be a conventional vacuum channel or groove such as, for example, a vacuum slot. The vacuum means should be adapted to handle flow rates/volumes of aqueous solution generally co"esponding to the flow rates/volumes out of the liquid deposition means.
The liquid deposition means and the vacuum means may be configured to deposit the ~queous solution on the permeable sheet in the general form of shapes, patterns, figures, alpha-numeric cl)aracl~l~, words, spots, pictures and the like. The vacuum means may contain a variety of configurations such as, for example, unevenly spaced vacuum slots or 10 slits (or shaped openings) designed to produce a gradient deposition. It is co"Lelnplaled that the liquid deposition means and the vacuum means could be configured to provide intemmittent deposition of aqueous solution on the permeable sheet so that step-wise or unit-wise operation may be achieved.
Upon appl' ~tion of the vacuum to a second surface (opposite the first surface to which 15 solution is initiafly conlacled) of the permeable sheet, a subaLanlidl portion of the aqueous solution containing altlph;,Jhilic ,,,ac,u,,,oleu~'-s (e.g., amphiphilic proteins) is drawn from the first surface and subsla,)Lially through the pemmeable sheet. This passage of the aqueous solution through the pemmeable sheet is generally thought to generate the shear stress con ~ ns necessary to provide appropriate levels of adsorption of al "pl ,iphilic 20 ma-;,u",e'sc~l'es (e.g., amphiphilic proteins) onto the individual exposed surfaces of the pemleable sheet.
Generally speaking, evacuation of the aqueous solution of amphiphilic ,,,ac,ùn,olecules (e.g., amphiphilic proteins) under vacuum levels described above to achieve suitable shear stress conc)ilions may be accom,~ hed with a sheet having a permeability of at least about 20 25 cfm/ft2, as measured for a sul,~lanlially dry sheet prior to being processed For example, the permeability of the sheet may range from about 50 to over 200 cfm/ft2, as measured for a subslanlially dry sheet prior to being prucessed. If a sheet has inadeq~ ~te pemmeability, the ~queous solution may puddle or pool on the first surface and may be non-ur,irol",ly concenl~aled, absorbed or diffused through the sheet. In such cases, it is generally thought 30 that saLisra~Lory conditions could be achieved by applying higher levels of vacuum, higher pressures andlor levels of force to the aqueous solution of amphiphilic ",ac~",c'ecules (e.g., amphiphilic proteins) contacting the permeable sheet and/or an applied gas pressure to drive the aqueous solution through the sheet thereby generating the apprupriaLe sheer stress conditions.
According to the present invention, it may be desirable to wash or rinse the pemmeable sheet after being contacted with the aqueous solution of amphiphilic ~"ac,u",~'ec~l'es (e.g., CA 02262~84 1999-02-02 W O 98/09016 PCT~US97tl2536 amphiphilic proteins). Washing or rinsing (not shown) the coated pemmeable sheet should be carried out using an aqueous liquid having a relatively high surface tension (e.g., water).
Although the volume of the liquid wash or rinse may vary greatly, it has been found that a volume of liquid rinse generally similar to the volume of aqueous solution of amphiphilic s pruteins may be sdtiaractory (e.g., from about 0.5 to about 1.5 times the volume of amphiphilic ",ac,ur"e'ec~r'e (e.g., amphiphilic protein) solution).
In general, the aqueous solution of amphiphilic ma.;,un,n'a~,ules (e.g., amphiphilic prul,,i.,s) should be able to flow freely. For example, the aqueous solution of amphiphilic "lac,u" ,o'ecl ~'es (e.g., amphiphilic pr.,teins) may have a viscosity of from about 0.1 to about 5 10 centipoise. Lower viscosity solutions appear to be desirable. However, it is conle",plaled that more viscous aqueous solutions could be used in the practice of the present invention provided that appruprial~ shear stress condiffons can be maintained by techr, ~ues including, but not limited to, applying higher levels of vacuum, higher pressures andlor levels of force to the aqueous solution and/or an applied gas pressure.
According to one embodiment of the invention, a substanlial portion of the aqueous solution of amphiphilic macromc'ecules (e.g., amphiphilic proteins) may be drawn through the sheet in less than about 1 or 2 seconds to generate the appropriate shear stress conditions for adso,~tion. For example, a substantial portion of the aqueous solution may be drawn through the pemmeable sheet in less than about 0.1 second. As a further example, a 20 sul,~ ntial portion of the aqueous solution may be drawn through the permeable sheet in less than about 0.01 second. As yet another example, a substantial portion of the ~queous solution may be drawn through the pemleable sheet in less than about 0.001 second. It is thought that appropriate shear stress conditions for adso,~ion of amphiphilic ,,,a~;,ulllnlecll~Es (e.g., amphiphilic p,-,tei.,s) may be encountered when the flow of aqueous solution has a 25 Reynold's number of at least about 200. For example, the flow of aqueous solution may have a Reynold's number of at least about 400.
In an i" ,pc" Ldnt aspect of the invention, the " ,alerial adsorbed on the individual ex,uosed surfaces of the permeable sheet are amphiphilic ~,ac,ul"~'ecues. Desirably, the amphiphilic r"ac,umc~ecues contain cJisc,~tely separated hydrophilic and hydrophobic regions. Such 30 amphiphilic mac~um2'ecu'es include, but are not limited to, synthetic polymers such as ionomers with separated areas of ionicity in an otherwise hydrophobic polymer, multiblock copolymers where every other block is highly charged or polar with the intervening blocks uncharged or nonpolar, protein, fatty acids, mucins, and other biological ",ac,o",o'e~l~'es with sepa,cled areas of hydrophilicity and hy.l,uphck.~
In another aspect of the present invention, the amphiphilic rnac,~",olecl~'es are amphiphilic prutei~s. Generally speaking, the amphiphilic pr~tei"s may be selected from CA 02262~84 l999-02-02 W O 98/09016 PCT~US97/12536 classes of globular proteins and/or random coil proteins. For e,~",zle, the amphiphilic proteins may be milk proteins. Desirably, the amphiphilic proteins may include pr~tei,)s such as those found in bovine milk including, for example, various caseins and whey protei"s.
Milk proteins (e.g., bovine milk proteins) have been identified as well-suited to provide a durable surface modification when applied to a pe~",~?'-'e substrate as describe above. The pr~tei. ~s in milk can be described as generally amphiphilic (i.e., they have both hydrophilic and hydrophobic regions) and tend to be surface active. Beta-casein (b-casein), one of the major milk proteins, is so surface active that it is used as an emulsifier in various food products.
Other milk proteins include, but are not limited to, b-lactoglobulins and whey pr~te;. IS.

EXAMPLES
SAMPLE PREPARATION
Experiments were conducted with four dir~e~enl types of surface-modified pemmeable cover materials. The four cover materials were: 1) milk protein treated polypropylene nonwoven web of meltblown fibers; 2) beta-casein treated polypropylene nonwoven web of meltblown fibers; 3) siloxane-polyether treated polypropylene nonwoven web of meltblown fibers; and 4) TRITON X-102 treated polypropylene nonwoven web of mel '~wn fibers.
Siloxane-polyether treated samples were used to assess the performance of a durable che", ~' surfactant treatment. TRlTON-treated samples were used as control and represent conventional "fugitive" surfactant treaL",enl~.
Milk-Protein Treated Nonwoven Webs Nonfat milk solutions of about 2.5 percent, by weight, nonfat milk were prepared by adding 25 9 of Camation~) Natural Nonfat Dry Milk (Nestle Food Company) solids to 1000 9 of distilled water and heating to approximately 70 degrees Centigrade. The resulting solution was stirred for 30 minutes and stored at 4 degrees Centigrade.
Solutions were generally allowed to equilibrate before being applied to pemmeable sheets of polypropylene nonwoven webs of meltblown fibers having a basis weight of about 1.5 osy (~51 gsm) available from Kimberly-Clark Corporation, Roswell, Georgia. Protein depocition was a~ ved by placing an 18.5 cm diameter disk of the nonwoven web in a large Buchner funnel appa,dlus and applying vacuum under the sample so that arp'i- ~' Ol1 of 500 mL of the 2.5 percent, by weight, nonfat milk solution covered the entire surface of the nonwoven web. The nonfat milk solution initially wet the nonwoven web within one second - and required an additional ten seconds to pass the entire volume of solution through the nonwoven web.
-CA 02262~84 l999-02-02 The nonwoven web was washed with 500 mL of distilled water while a vacuum was applied. The nonwoven web was allowed to dry at ambient temperature and the dry add-on of nonfat milk was measured to be approximately 0.38 percent, by weight.
Beta-Casein Treated Nonwoven Webs Polypropylene nonwoven webs of meltblown fibers (basis weight of about 1.5 osy or ~51 gsm) were treated with beta-casein in acco,dance with the procedure described above.
Deposition of beta-casein was accorr,pl:~hed using 200 mL of a 0.5 percent, by weight, ~queous solution of beta-casein. Like the nonfat milk solutions, the beta-casein solutions also initially wet the polypropylene nonwoven webs of meltblown fibers within one second. One 10 sample was rinsed with water as above while the other was left unrinsed to test the role of the treatment's permanence in blood wicking and fluid surface tension reduction. The dry add-on of beta-casein for the rinsed samples were measured to be approximately 0.10 percent, by weight.
Durable Surfactant Treated Nonwoven Web Polypropylene nonwoven webs of meltblown fibers (basis weight of about 1.5 osy (~51 gsm) with a durable sulrautanl treatment (siloxane polyether) were prepared by vacuum ekl,~cLion with a water rinse generally in accordance with the procedure described above.
Deposition of siloxane polyether was accor"plisl1ed using 400 mL of 0.2 percent, by weight, aqueous solution of siloxane polyether TEGOPREN@) 5830 (Goldschmidt Chemical Company, Hopewell, Virginia). The dry add-on of durable s~"rdctanl was measured to be approximately 0.36 percent, by weight.
Fuqitive SLJI r~ctanl Treated Nonwoven Web Polypropylene nonwoven webs of meltblown fibers (basis weight of about 1.5 osy (~51 gsm) with a su,raclant treatment (an octylphenoxypolyethoxyethanol nonionic surfactant, available under the trade designation "TRITON X-102" from Union Carbide Corporation, Danbury, Connecticut) were pr~pared by soaking 7 inch by 10 inch samples of the nonwoven web for 2 minutes in 500 mL of an a~ueoll~ solution of 0.125 percent, by weight, of TRITON
X-102. The soaked sa"~,:les were nipped in an Atlas Laboratory Wringer (at 30 pounds pressure~ and hung under a fume hood to dry at ambient conditions. The dry add-on of fugitive su~ra.,~"l was measured to be approximately 0.65 percent, by weight. It should be noted that vacuum extraction treatment for the TRITON X-102 sar",-!es was not used because the surfactant's lack of durability on the polypropylene substrate would likely cause it to be washed away during sample p,~paraLon.

CA 02262~84 1999-02-02 SAMPLE CHARACTERIZATION
Protein Deposition X-ray Photoelectron sPectroscopy: X-ray Photoelectron Spe~ l,uscopy (XPS) data were ~ "osted using a Surface Science Labs M-Probe ESCA with monocl"u",alic aluminum Ka radiation. All sam~ 'e s were mounted on double-side adhesive tape and chargeneutralized with a 0.5 eV electron flood. Binding energies were referenced to C(1s) for hy.l,ucd,L,on at 284.6 eV for charge compensation. XPS-detert~'E nibùgen was monitored to detemmine the nature of the coating and also to monitor the dependence of protein deposition on concenL~tion shear and solvent washes.
Scannin~ Electron Mior~scopy: Field emission scanning electron mic,uscopy analyses were ca~ied out using a Hitachi S4500 field emission scanning electron mi.;,uscope.
Stainin~/OPtical M;cluscoPy: For polarized light microscopy sarr,~ los were stained with ninhydrin spray reagent (0.2% ninhydrin in ethanol Sigma Chemical Company) and dried at 55~C until a definite purple color developed on controls. Samples were then observed with 15 I,ansmiLIed polarized light using a Zeiss polarized light microscope. Some sa", l~s were stained with Alizarin Red S (Aldrich Chemical Company Inc.) by soaking treated sa",r'o~s in approximately 25 mL of 200 ppm alizarin in aqueous solution until a red color developed.
These Sdlll~lQS were rinsed with water and ar"':'~nLly dried.
For fluor~scence optical microscopy sar" 9o~ were treated with protein-specific 20 fluo,~:sca"line spray reagent (0.05% fluorescamine in acetone Sigma Chemical Company) and immediately treated with 25 percent by weight ammonia (spray) to increase fluor~scence intensity. After drying an,''enLly the samples were observed using a Leitz Fluovert inverted microscope with R~ 1ion by long wavelel1gl1, UV light (355-425 nm).

Coating Durability The durability of the protein coatings was tested by e~posing coated 5~1"~'~S of the ".c"' '~Jn polypropylene web to various liquids/solutions and conditions i"lended to remove the co~Lings.
Solutions described below were passed through individual milk-protein treated Ill.o"''~wn polypropylene webs having a diameter of about 25 mm. Individual samples were held in a syringe disk filter and rinsed with one of the following:
20 mL distilled water 10 mL 5 percent by weight acetic acid 10 mL 0.5M HCI
10 mL 300 ppm TRITON X-102.

CA 02262~84 1999-02-02 W O98/09016 PCTrUS97112536 Samples were then rinsed with distilled water and dried at a",'~ ~nl conditions.In addition, individual milk-protein treated meltblown polypropylene web sam,-'es having a diameler of about 25 mm were treated by 10 minutes of sonication in ethanol or boiling in 10 mL 1 percent, by weight, sodium dodecyl sulfate. Samples were then rinsed with distilled water and dried at ambient conditions.
XPS was used to determine the presence of protein on the surface of the meltblowpolypropylene web sa~ I ~r 85.

W~'' ' .' 'y and SurFace Energy lOContact Anqle Measurements: Contact angles of sessile drops of whole and nonfat milk solutions on a polypropylene film were detemmined using a Rame-Hart, Inc. goniometer (model number 100-00 115) equipped with a videocamera.
Fluid Surface Tension Reduction: Meltblown polypropylene webs having a basis weight of 1.5 osy (51 gsm) available from Kimberly-Clark Co,,uor~lion were milk-protein treated.
15Samples measuring app~uximalely 2" x 3" were soaked for 24 hours in 80 mL of deionized water. The surface tension of the water was measured before and after sample soaking via the DuNouy ring method to detemmine if wetting of the material occurred via fluid surface tension reduction or by some other mechanism.
Critical Surface Tension of Wettinq Measurements: Appro~i" ,alions of the critical surface tension of wetting of the milk-protein-treated rllaterials were made by testing water wettability and by using wetting tension fluids available from Pillar Technologies, Inc. of I la, lland, Wisconsi". Sessile drops of the wetting fluids were placed on milk-protein-modified meltblown polypropylene webs in order of decreasing surface tension. The surface tension of the first drop to spread on the surface of the treated web within 2 seconds yielded an 25 approximalion of the treated web's critical surface tension of wetting in dynes/cm (which may be c~"~laled to an approximation of surface energy). See, Bennet, M.K. and Zisman, W.A.;
Relation of WettabilitY by Aqueous Solutions to the Surface Constitution of Low EneraY
Solids; J. Phys. Chem., pps. 1241-1246, Volume 63 (1959). The surface tensions of the fluids used in this analysis ranged from 50 to 70 dynes/cm. This analysis did not spatially resolve 3 o any coating anisûlropy in the x, y-direction (patterning).

Blood wicking studies Blood wicking performance of polypropylene nonwoven webs of meltblown fibers having various applied surface treatments was measured using the procedure described CA 02262~84 1999-02-02 W 098/09016 PCTrUS97/12536 below. Fresh bovine blood was used in all studies. The hematocrit of initial investigations was not measured, but that of subsequent investigations was corrected to 30 percent.
Samples of polypropylene nonwoven webs of meltblown fibers (basis weight of approximately 1.5 osy (- 51 gsm) were cut to dimensions of 3 inches by 7.5 inches, with 5 the length aligned with the machine-direction of the nonwoven web. The samples were placed over a Kotex~) Maxi pad (available from Kimberly-Clark corporation) that was modified by removing the conventional pad cover material. The modified pad and the experimental cover were each weighed separately. The pad and cover were placed on a colostomy bag (mounted on a lab jack) and were raised to contact a sheet of Plexiglas in 10 order to adjust the applied pressure to 0.3 psi. Bovine blood was passed through an 18 gauge ~1/32" diameter) orifice in the Plexiglas directly above the cover at a rate of 4 mUhour (controlled by an infusion pump). The stain dimensions were recorded periodically throughout the experiment. At the completion of the experiment, photographs and weights of the cover and pad were obtained.
EXPERIMENTAL RESULTS
CG~ ;OI~ Of Protein Deposilic~l) Milk protein modification of the meltblown fiber surface of the nonwoven polypropylene web was confirmed using fluorescence optical microscopy and XPS
20 analyses. Fluorescence optical microscopy and scanning electron microscopy (SEM) indicated a coating which lies on the individual fibers of the nonwoven web and is not entrained in fiber intersections. XPS-detectable nitrogen values of the milk-protein treated surfaces ranged from 5-12% as summarized in Table 1. The unifommity of protein coating for the milk protein-treated polypropylene meltblown nonwoven web (~Yposed to 25 protein in a non-homogenous shear field using the Buchner funnel procedure described above) was assessed by measuring XPS nitrogen intensity sy~l~r"dtically at various spots on the nonwoven web surface. The results tabulated in Table 2 show the spot-to-spotagreement, sugges~ing a relatively uniform presence of a protein coating on the nonwoven web surface. FESEM micrographs (FIG. 1) co"ubordle these data, indicating a thin, 30 tenacious coating which is relatively unifomm along individual fibers and is not aggregated at fiber intersections. Apparent heterogeneity in the coating thickness in the FESEM micrograph is believed to result from differences in protein thickness and not from the presence of unmodified polypropylene.
However, when these coatings are stained (ninhydrin and Alizarin Red S) in bulk and 35 observed macroscopically, a polka dot pattern is evident over the surface of the filter, as CA 02262~84 1999-02-02 WO 98tO9016 PCT/US97112536 shown in FIG. 2. The polka dot pattem shown after staining corresponds to the holes in the Buchner funnel used in the vacuum deposition of the milk prutei. ,s. The holes in the funnel produce areas of high shear stress.
The agreement obtained for various analysis areas (XPS) over the surface of the milk-protein-treated samples suggests complete surface coverage, but bulk staining (ninhydrin) of the samples indicates a non-homogeneous coating, showing a polka-dot pattern of deposition which corresponds to the holes in the Buchner funnel used during the deposition. Taken together, the XPS results suggesting cG,nplete surface coverage and the bulk staining results indicating a non-homogeneous coating, suggest the surface 10 of the nonwoven web is protein covered with isolated regions of greater deposition resulting from the shear dependence of the protein deposition and which cause patterned staining (and wettability, as discussed below).

Durable And Zoned Surface Treatment 15 Durability of the milk protein modification was tested against several solvents. The only method atle",,~)led which reliably removed the milk proteins from the polypropylene surface was 10 minutes exposure to boiling 1 percent, by weight, sodium dodecyl sulfate solution.
The solvents used were (a) water; (b) ethanol; (c) 300 ppm TRITON X-102 solution; (d) 0.5 M
HCI; (e) 5 percent, by weight acetic acid; and (f) 1 percent, by weight, sodium dodecyl sulfate solution. The results are s~" ""~arked in FIG. 3.
Milk protein-treated nonwoven polypropylene webs of meltblown fibers were not inslar,lly wettable by water or blood. However, they did wet within 5-10 seconds with a critical surface tension of wetting of approximately 60 dynes/cm. As summarized in Table 4, vacuum extraction of nonfat milk or 13-casein solutions through the nonwoven web (followed by copious water rinsing) result in a material which was slowly wettable to water without a significant decrease in the water surface tension. This stands in contrast to traditional surfactant-treated materials which showed a decrease in the "final" water surface tension. That result suggests the milk-protein treatment method results in wettability by raising the apparent surface free energy of the material and not by reducing the surface tension of the wetting fluid. This wettability was observed to occur only in isolated regions of the protein treated substrate (i.e., in the polka-dot pattemcorresponding to the holes in the Buchner funnel and observed via ninhydrin staining).
In addition, milk protein treated nonwoven polypropylene webs of meltblown fibers were soaked in 80 mL deioni~ed water for 24 hours to detemmine if any surface tension reduction could be measured for the wash solution. As shown in FIG. 4, the surface tension of the water prior to and after sample soaking was measured at 72 dyneslcm, indicating the , CA 02262~84 1999-02-02 W O 98/09016 PCTAUS97tl2536 absence of any b-casein at a concel1l,dlion of greater than about 5 ppm in the solution after washing.
In comparison, the unrinsed r~-casein-treated sample lowered the water surface tension by nearly 13 dynes/cm and was uniformly wetted by soaking in water. ît is likely that the excess protein left in the nonwoven web (not rinsed away during preparation) dissolved in the wetting fluid and promoted uniform wetting, similar to the behavior observed for traditional surfactant treatments. Investigations of the wettability of the nonwoven web samples treated by vacuum extraction of a durable surfactant (siloxane polyether TEGOPREN~ 5830) also demonstrated uniform wetting of the treated material.
Coupled with the XPS results which indicate the protein coating's substantiveness to water wash, these results stongly suggest that water wettability can be attributed to an increase in the surface free energy of the meltblown polypropylene nonwoven web instead of a decrease in the surface tension of the wetting fluid, characteristic of a durable protein coating. The wettability also occurs in the polka dot pattern observed during staining, which may be favorable in the control of fluid flow in absorbent structures and most likely results from the shear dependence of milk protein deposition.

Sided Surface Treatment A sidedness or gradient distribution to the deposition can be observed, especially on higher basis weight nonwoven webs. A gradient distribution of protein coating is defined as that condition when the collective concentration of protein on individual exposed surfaces (e.g., individual fiber surfaces) within one length element of the pe""eable sheet (e.g., nonwoven fabric) is ~lifrer~nt than the collective protein concer,l,dLion on an equal number of individual exposed surfaces (e.g., individual fiber surfaces) contained in an acljacenl, equally~5 sized element. The gradient distribution may be expressed by the following equ~tion:
d[P]/d[t] ~ 0 Where P is the total protein concenl,alion and t is the length element over which the protein concenL,dlion is measured. The total protein concenl,dlion (P) can be measured in the two orthogonal directions parallel to the surface or in the thickness direction (i.e., X, Y or Z
gradients) For a matrix of fibrous material, the dimensions of t are on the order of integral multiples of fiber diameters. For example, t can be five fiber diar"et~r~. If the fibrous material is meltblown fibers, t is app,uki",alely 25 microns.
Difre,ences in the XPS-detectable nitrogen between the top and bottom of milk-protein treated salll~ s indicate this sidedness, as do measurements of the appar~nl surface free energies of all milk-protein treated "ldlerials as shown in Table 1.

CA 02262~84 1999-02-02 W O 98/09016 PCTrUS97/12536 As another example a 18.5 cm diameter disk of 1.5 osy polypropylene meltblown nonwoven web ~thickness 35 microns) was contacted with 1200 mL of a 2.5 percent by weight milk protein solution followed by a rinse with 600 mL of distilled water.Table 3 s~""",ari~es data showing a gradient distribution or sidedness as indicated by dirre,~nces in XPS-detectable nitrogen and surFace free energies (e.g. 11% and 60 dynes/cm (top) vs. 6% and 50 dynes/cm (bottom)). Untreated meltblown polypropylene nonwoven web has a surface energy of about 36 dynes/cm and no XPS detectable nitrogen (i.e. <0.2 atom %). Analysis shows that the concentration of protein on the surface of the fibers is higher on the top side relative to the bottom. A top to bottom gradient is established.
10 The apparent surface energy determined by the maximum solution surface tension to wet the fabric, is higher on the top surface. This difference in apparent surface energy is manifest in a greater extent of water wettability for the top surface and most likely results from the higher surface concentration of protein.
Additionally the top side and the bottom side of the treated meltblown polypropylene nonwoven web was stained with Alizarin Red S. The top side exhibited high optical density and the bottom side exhibited low optical density. Re~use only the protein coating reacts with the red stain the darker color (i.e. high optical density) further co"ubora~es the presence of more protein on the top surface of the nonwoven web.
Taken together these results strongly suggest that regions of greater protein deposition exist on the nonwoven substrate and these regions correspond to the pattern in the vacuum lion "box" that was placed under the nonwoven substrate. The data also show a gradient of protein deposition through the polyolefin web which is manifest as a sidedness.
This sidedness was not observed for sam~!es treated by vacuum exL,d- lion of a durable s~"fac~anl (siloxane polyether TEGOPREN@) 5830) as shown in Table 1.

Results Of Controlled Wettability-Blood Wicking Studies The spatially-controlled wettability imparted to nonwoven webs of meltblown polypropylene fibers treated by vacuum extraction of protein solutions appears to have direct consequences on the transfer of blood through a nonwoven web as illustrated in FIGS. 5A and 5B and Table 5.
FIG. 5A is a composite of two photographs (not to scale) of the absorbent pad with a milk-protein treated bodyside permeable cover. The left side of FIG. 5A shows the cover surface while the right side of the FIG. 5A shows the surface of the absorbent pad (which was located underneath the cover) as well as the backside of the cover. It should 35 be noted that results shown in FIG. 5A were produced with the cover material oriented so .

CA 02262~84 1999-02-02 W O 98/09016 PCTAUS97/12~36 that the side of the cover material exhibiting the higher critical surface tension of wetting was on the upper, top, or bodyside location. Blood wicking time was 45 minutes. As clearly seen in FIG. 5A, there is a lack of blood on the surface of the cover. Most of the blood is in the absorbent material underneath the cover.
The milk-protein treated cover shown in FIG. 5A exhibited some initial delay to blood wetting, which resulted in initial blood puddling (1.25 cm x 2.25 cm, all stain sizes are given as machine direction 'MD' x cross-machine direction 'CD'). This initial stain did not increase in size during the experiment, but other spots arose from rewet of the cover from the absorbent underneath. Total blood retention in the cover (relative to the total l0 amount of blood in pad and cover) was 0.4 percent, by weight. Deposition of milk proteins on the polypropylene nonwoven web via vacuum extraction has clearly improved the transfer of blood away from the surface of the nonwoven web (used as a permeable, bodyside cover material) resulting in less surface staining and blood retention. Although the inventors should not be held to a particular theory of operation, the favorable blood 15 transfer characteristics of the milk-protein-treated nonwoven web of meltblown polypropylene fibers are believed to result from the spatially-controlled wetlabili~y of the treated material imparted by the gradient or graduated coating of protein on the low surface energy polypropylene substrate.
FIG. 5B is a composite of two photographs (not to scale) of the absorbent pad with 20 the TRITON X-102 treated bodyside, permeable cover. The left side of FIG. 5B shows the cover surface, while the right side of the FIG. 5B shows the surface of the absorbent pad (which was located underneath the cover) as well as the backside of the cover. The TRITON X-102 treated cover was thought to have generally the same level of wettability on each side so that orientation of the cover was not considered significant factor 25 affecting the ability of blood to pass through the thickness (Z-direction) of the cover.
Blood wicking time was approximately 31 minutes.
In comparison to the milk-protein treated cover (FIG. 5A), the TRITON X-102-treated cover (FIG. 5B) developed an immediate stain which resulted from spreading of blood on the cover surface with a stain dimension of 5.1 cm x 4.4 cm and total blood 30 retention in the cover of 3.6 percent, by weight.
Another experiment was conducted utilizing a sample of the 1.5 osy (~51 gsm) nonwoven web of polypropylene meltblown fibers with no surface modi~ica~ion treatment of any kind as the bodyside cover material for an absorbent pad as described above. No photog,dphs of the results of this experiment are shown. The untreated polypropylene 35 cover material exhibited no blood wettability at all, even under an applied pressure of 0.3 psi. The blood spread over the surface of the nonwoven web and off of the pad, with CA 02262~84 l999-02-02 negligible blood retention and transfer. Orientation of the web did not affect the spreading of the blood in the x,y-direction during these experiments.
Samples with and without fugitive protein present were investigated in the bloodwicking studies. Results of these studies are shown in FIGS. 6A and 6B. FIG. 6A is a composite of two photographs (not to scale) of the absorbent pad with a beta-casein treated bodyside, permeable cover. The left side of FIG. 6A shows the cover surface, while the right side of the FIG. 6A shows the surface of the absorbent pad (which was located underneath the cover) as well as the backside of the cover. FIG. 6B shows the same types of photographs for an unrinsed 13-casein treated sample. It should be noted 10 that results shown in FIGS. 6A and 6B were produced with the cover material oriented so that the side of the cover material exhibiting the higher critical surface tension of wetting was on the upper, top, or bodyside location. Blood wicking time for results shown in each of FIGS. 6A and 6B was 45 minutes.
The 13-casein treated cover material shown in FIG. 6A was prepared via vacuum 15 extraction and rinsed to remove excess protein. As can be seen from FIG. 6A, the cover yielded results very similar to those obtained for the similarly prepared milk-protein-treated sample, with a small initial stain (1.~ cm x 5.25 cm) which did not spread over the course of the experiment and total blood retention in the cover of 0.8 percent, by weight.
The initial spread of the stain along the width of the pad was caused by a delay in 20 wetting of the cover by the initial blood insult. Once the cover was wetted, there was no additional spreading on the cover surface.
As can be seen in FIG. 6B (and by comparison to FIG. 5B), the unrinsed l~-caseinsample exhibited properties remarkably like those of TRITON X-102. The stain spread on the cover surface during the course of the experiment and had final dimensions of 25 3.75 cm x 7.0 cm. Total blood retention in the cover was 6.1 percent, by weight. This similarity to TRITON X-102 treated samples likely resulted from the fugitivity of excess protein in the nonwoven web causing fluid surface tension reduction and allowingspreading.
These blood wicking results are qualitatively very similar to the water wellability 30 results given above and indicate that the combination of zoned and durable wettability, rather than just simple protein modification, renders the lateral spreading of blood unfavorable and results in better z-direction transfer of blood into the absorbent core underneath.
This z-directional transfer can also be assisted by the sidedness imparted to the 35 treated material by vacuum extraction of milk proteins, as illustrated in FIGS. 7A and 7B.
The left sides of both figures show the cover surface, while the right sides of both figures CA 02262~84 1999-02-02 W O 98/09016 PCTrUS97/12536 show the surface of the absorbent pad (which was located underneath the cover) as well as the backside of the cover. FIG. 7A is a composite of two photographs (not to scale) of the absorbent pad with a milk-protein treated bodyside, permeable cover. Results shown in FIG. 7A were produced with the cover material oriented so that the side of the cover material exhibiting the higher critical surface tension of wetting was on the upper, top, or bodyside location. Results shown in FIG. 7B were produced with the cover material oriented so that the side of the cover material exhibiting the lower critical surface tension of wetting was on the upper, top, or bodyside location. Blood wicking time for results shown in each of FIGS. 7A and 7B was 45 minutes.
As can be seen in FIG. 7A, a stain caused by initial puddling of the blood occurred on the side of the sample exhibiting the higher critical surface tension of wetting (which was oriented upward). The stain caused by this puddling did not increase in size over the course of the experiment and had a final dimension of 2.5 cm x 3.25 cm, with total blood retention in the cover of 1.9 percent, by weight.
In comparison, the sample in FIG. 7B was placed so that the side of the sample exhibiting the lower critical surface tension of wetting was positioned upward. In this case, the stain observed resulted entirely from rewet of the cover from the absorbent underneath. Only a minuscule (2 mm x 2 mm) stain occurred on the cover surface from the initial blood contact. The stain caused by rewet of the cover resembled a polka-dot 20 pattern and was 4.5 cm x 4.0 cm in size with total blood retention in the cover of 4.8 percent, by weight.
ESCA data and critical surface tension of wetting results in Tables 1 and 3 strongly suggest that the protein coating exhibited sidedness on the polyolefin web. It is generally thought that a gradient distribution of protein deposition exists throughout the depth of 25 the polyolefin web. This gradient distribution of protein deposition is also thought to provide a graduated level of wettability into the depth (i.e., Z-direction) of the polyolefin web.
Such an increasing level of wettability into the depth or Z-direction of a permeable, bodyside cover material for an absorbent personal care product appears to promote 30 preferential flow toward the area of higher wettability and into the absorbent pad underneath, allowing for less surface pooling and staining (at least under forced flow conditions). Accordingly, the expression "controlled wettability" refers to an increasing level of wettability along at least one dimension of permeable material (which otherwise would have relatively low surface energy). This increasing level of wettability (i.e., 35 "controlled vveLLabil;Ly") along at least one dimension of the permeable material is thought to correspond to an increase in surface energy along this dimension of the permeable CA 02262~84 1999-02-02 material, which is due to a graduated level of protein deposition. The present invention should not be limited only to a "graduated" level of protein distribution. It is contemplated that controlled distribution of protein deposition or amphiphilic macromolecule deposition along at least one dimension of the permeable sheet may be in the form of a linear gradient distribution, a "step-function" type distribution or the like.
The "conL~ollcd wettability" or preference for flow toward areas of higher wetlability resulted in blood retention on the side of the cover material with a higher critical surface tension of wetting (See, for example, FIGS. 7A and 7B). This effect may be used to control stain location and appearance as well as fluid distribution.
While the present invention has been described in connection with certain preferred embodiments, it is to be understood that the subject matter encompassed by way of the present invention is not to be limited to those specific embodiments. On the contrary, it is intended for the subject matter of the invention to include all alternatives, rnoc~iricalions and equivalents as can be included within the spirit and scope of the following claims.
I

CA 02262~84 1999-02-02 W O 98/09016 PCTrUS97/12536 Table 1 Summary of XPS and Critical Surface Tension of Wetting Measurements CST, dynes/cm XPS atom% Nitro~en (+ 1 %) (t2 dYnes/cm) A

Sample Topb Bottom ToDb Bottom PP MB None None 36 36 Control Milk-protein 7.0 4.9 60 50 treated 13-casein 8.4 Not Measured 60 42 treated, rinsed l~-casein, not rinsed 11.7 NotMeasured 64 50 TRITON X-102 treated N/A N/A WWC Not Measured Siloxane polyether N/A N/A 40 38 TEGOPREN~3 5830d a CST = Critical Surface Tension of Wetting. Values reported were observed for several spots over the entire treated PP surface; the measurements did not spatially resolve the presence of the polka-dot pattern observed in staining.
b The top of the sample refers to the side of the PP MB with initial contact with solutions.
The bottom is the side in direct contact with the surface of the Buchner funnel. It is the top side of the sample which exhibits greater deposition and higher critical surface tensions of wetting.
c WW = water wettable d Siloxane polyether results are reported here to demonstrate that there is not a sidedness to this durable surfactant's deposition. XPS detectable silicon was monitored (top and bottom) in this case and was 8.5 atom% and 8.3 atom%, respectively.

. ~

CA 02262~84 1999-02-02 WO 98109016 PCTtUS97tl2536 Uniformity of Milk Protein Coating on Filter Surface SamPle Positiona % Nitroqen %Nitro~en/%Carbon A 11.3 0.15 B 11.4 0.15 C 11.3 0.15 D 10.8 0.14 E 10.5 0.14 F 10.5 0.14 G 11.4 0.17 H 11.6 0.16 10.4 0.14 J 11.7 0.16 a Sample positions across a 49-mm diameter, milk protein treated, 0.5 osy polypropylene meltblown (PP MB) filter. The analysis was perfommed on the top side of a second disk exposed to 50 mL 2.5 percent, by weight, nonfat milk solution. The second exposure was used to eliminate the contribution of any mechanically-trapped particles to XPS-det~ct~ nitrogen. Only carbon, nitrogen, and oxygen were detected on the filter surface.

r~

CA 02262~84 1999-02-02 Sidedness of Milk Protein Deposition on PP MB

XPS % Nitro~en XPS N/C Ratio SamPle ToP Bottom Top Bottom 0.5 osya 11.1 5.7 0.15 0.07 11.8 9.5 0.17 0.12 1.5 osyb 11.0 6.0 0.15 0.07 a Milk protein treated PP MB was made by passing 50 mL of 2.5 percent, by weight, nonfat milk solution through a 49-mm diameter 0.5 osy PP MB disk, followed by a rinse with 200 mL distilled water.
b Milk protein treated PP MB was made by passing 1200 mL of 2.5 percent, by weight, solution through a 18.5-cm .lia",eler 1.5 osy PP MB disk, followed by a rinse with 600 mL of distilled water. Surface energies of the 1.5 osy PP MB were 60 dynes/cm and 50 dynes/cm for the top and bottom, respectively.

Table 4 Wetting Fluid Surface Tension Reduction Studiesa Water Surface Tension, dynes/cm (+1 dyne/cm) SamPle Initial Final Milk-protein-treated 72.6 71.3 13-casein-treated, rinsed 72.7 71.3 13-c-asein-treated, unrinsed 72.6 59.7 Surface tension reduction measurements were made using the DuNouy ring method.

CA 02262~84 1999-02-02 Table 5 Blood Transfer Properties of Treated Materialsa % Total Blood Retained Sample Side ExPosed to Bloodb in Cover(+0.2%) Milk-protein treated Topb 1.0 Miik-protein treated Bottom 4.8 13-casein-treated, rinsed Top 0.8 13-casein-treated, unrinsed Top 6.1 TRITON X-102-treated Top 3.6 a Blood wicking studies were carried out as described in the text. Blood wicking time for all samples shown was 45 minutes, with the exception of the TRITON X-102-treatedsample, which had a blood wicking time of 30.7 minutes.
b The top of the sample is as described in Table One.

Claims (25)

WHAT IS CLAIMED IS:

1. A permeable, liquid flow control material comprising:
a permeable sheet having a plurality of individual exposed surfaces, at least a portion of which have a surface energy of less than about 45 dynes/cm;
amphiphilic proteins adsorbed onto at least some individual exposed surfaces to define a gradient distribution of amphiphilic protein coating along at least one dimension of the permeable sheet, and wherein the adsorbed amphiphilic protein coating provides controlled wettability along at least one dimension of the cover material.

2. The permeable, liquid flow control material of claim 1 wherein the amphiphilic proteins are adsorbed on the permeable sheet such that the cover material is substantially free of fugitive amphiphilic proteins.

3. The permeable, liquid flow control material of claim 1 wherein the amphiphilic proteins are adsorbed onto at least some individual exposed surfaces thereby defining a patterned protein coating on the permeable sheet.

4. The permeable, liquid flow control material of claim 1 wherein the coating ofamphiphilic proteins uniformly adsorbed onto individual exposed surfaces is present in only discrete portions of the sheet material.

5. The permeable, liquid flow control material of claim 1 wherein the amphiphilic proteins are selected from the group consisting of globular proteins and random coil proteins.

6. The permeable, liquid flow control material of claim 1 wherein the amphiphilic proteins are milk proteins selected from the group consisting of .beta.-casein, .beta.-lactoglobulin and whey proteins.

7. The permeable, liquid flow control material of claim 1 wherein the cover material has a liquid retention of less than about 5 percent, by weight.

8. The permeable, liquid flow control material of claim 1 wherein the cover material has a liquid retention of less than about 3.5 percent, by weight.

9. The permeable, liquid flow control material of claim 1 wherein the coated sheet has a critical surface tension of wetting greater than about 50 dynes per centimeter.

10. The permeable, liquid flow control material of claim 1 wherein the coated sheet has a critical surface tension of wetting greater than about 60 dynes per centimeter.

11. The permeable, liquid flow control material of claim 1, wherein the gradientdistribution of amphiphilic protein coating is along at least two dimensions of the permeable sheet.

12. The permeable, liquid flow control material of claim 11, wherein the adsorbed amphiphilic protein coating provides controlled wettability along at least two dimensions of the permeable sheet.

13. The permeable, liquid flow control material of claim 1, wherein the permeable sheet is a matrix of fibrous material.

14. The permeable, liquid flow control material of claim 13, wherein the nonwoven fabrics are selected from nonwoven webs of meltblown fibers, nonwoven webs of continuous spunbond filaments and bonded carded webs.

15. The permeable, liquid flow control material of claim 13, wherein the nonwoven web of meltblown fibers further includes one or more secondary materials selected from the group consisting of textile fibers, wood pulp fibers, particulates and super-absorbent materials.

16. The permeable, liquid flow control material of claim 13, wherein at least a portion of the fibrous material is a bi-component material selected from bi-component fibers and bi-component filaments.

17. The permeable, liquid flow control material of claim 1, wherein the permeable sheet is an apertured, film-like material.

18. The permeable, liquid flow control material of claim 1, wherein the material is a liquid intake material.

19. The permeable, liquid flow control material of claim 1, wherein the material is a liquid distribution material.

20. The permeable, liquid flow control material of claim 1, wherein the material is a liquid retention material.

21. A permeable, bodyside cover material for absorbent personal care products, the cover material comprising:
a permeable sheet having a plurality of individual exposed surfaces, at least a portion of which have a surface energy of less than about 45 dynes/cm;
amphiphilic proteins adsorbed onto at least some individual exposed surfaces to define a gradient distribution of amphiphilic protein coating along at least one dimension of the permeable sheet, such that the cover material is substantially free of fugitive amphiphilic proteins, and wherein the adsorbed amphiphilic protein coating provides controlled wettability along at least one dimension of the cover material.

22. The permeable, bodyside cover material of claim 21, wherein the gradient distribution of amphiphilic protein coating is along at least two dimensions of the permeable sheet.

23. The permeable, bodyside cover material of claim 22, wherein the adsorbed amphiphilic protein coating provides controlled wettability along at least two dimensions of the permeable sheet.

24. A permeable, liquid flow control material comprising:
a permeable sheet having a plurality of individual exposed surfaces, at least a portion of which have a surface energy of less than about 45 dynes/cm;
amphiphilic macromolecules adsorbed onto at least some individual exposed surfaces to define a gradient distribution of amphiphilic macromolecule coating along at least one dimension of the permeable sheet, such that the cover material is substantially free of fugitive amphiphilic macromolecules, and wherein the adsorbed amphiphilic macromolecule coating provides controlled wettability along at least one dimension of the cover material and wherein the cover material has a liquid retention of less than about 3.5 percent, by weight.

25. The permeable, liquid flow control material of claim 24, wherein the amphiphilic macromolecules are selected from ionomers with separated areas of ionicity in an otherwise hydrophobic polymer, multiblock copolymers where every other block is highly charged with the intervening blocks uncharged, amphiphilic proteins, fatty acids, mucins, and biological macromolecules with separated areas of hydrophilicity and hydrophobicity.