CA2257170A1 - Absorbent footwear material - Google Patents
Absorbent footwear material Download PDFInfo
- Publication number
- CA2257170A1 CA2257170A1 CA 2257170 CA2257170A CA2257170A1 CA 2257170 A1 CA2257170 A1 CA 2257170A1 CA 2257170 CA2257170 CA 2257170 CA 2257170 A CA2257170 A CA 2257170A CA 2257170 A1 CA2257170 A1 CA 2257170A1
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- Canada
- Prior art keywords
- foam
- polyol
- polymer
- polyurethane foam
- hydrophilic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/142—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer
- D06N3/144—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer with polyurethane and polymerisation products, e.g. acrylics, PVC
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
- D04H1/68—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions the bonding agent being applied in the form of foam
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/04—Processes in which the treating agent is applied in the form of a foam
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
An open cell polyurethane, non-swelling foam impregnated or coated into a non-woven fabric, comprising super absorbent ingredient particles. The disclosed material is a super absorbent, fluid locking, moldable footwear product that takes body fluids away from the surface, and gels or locks the fluids in place even while under pressure. The material is breathable and releases fluids through evaporation.
Description
W O 97/45206 PCT~US97110216 A~RSO RRE~r FOOl~EA~R M~ F~-A~
10 Field of the Invention This invention relates to a liquid locking, moldable, non-swelling, polyu~lhdllefoam i~lly~g~ eA into a non-woven fabric. More particularly, it relates to a durable, liquid abso.l~n~, non-swelling, col-~y~,ssion moldable composite mqtPriql ehat locks in fluids when su~je~l~d to pl~S~lc.
R~~ru~d of the Invention The problem of moisture collectin~ in shoes, boots, and other footwear has long been a problem in the footwear art. Moi~re released by the foot, if not wicked away, can cause discclllfoll, tt;ll~yel~llulc ~ n~es~ blisters, and fungus growth.
Typically, the moisture yl~ has been addressed by h~colyo,~ling a mni~lre-wiC~ing liner in the footwear product. Such liners are often made from textile and nonwoven mqttqriq1~ or a combillali~n of both.
Foam footwear insoles are well-known in the art, typically being co~ ,ised of a ~ te conlplisi"g a liner mqfPri~l as a top layer, a foam or other cushioning mqtçri~l, 25 and a slirr~ner un-le~ the foam and liner layers. The foams are typically polyul~ e or polyethylene foams. Current footwear insoles foams are resilient and provide a shock-c(~ ents of the insoles of the prior art do not provide for wicking of moisture away from the foot and subse~luenl locking of the moisture in the insole.
The use of foams made from hyd~llilic polymers as cu~hinl ing and absorptive insoles for footwear is one possible solution to the above problem. However, S footwear insoles co..~ d of foams made from hyd~hilic polymers have ~ignifi(~nt disadvq-nt-a~es. Swelling occurs upon liquid absorption in almost all polymeric foam compositions made from hydlu~llilic polymers. In these foams, i.e., those which use a hydlophilic polymer, absol~Jtion takes place ~n the polymer, which 11IG1~;rU1~ swells. The swelling ~ fi~1res the thw~np~ss of the product, which is a pl~- n in the limited volume of lO a shoe cavity. Further, c1-~n~s in f1;~ nA;~ of the foam can cause stress on the junction of the foam with the other e1~ of the foolw~ mqtPriq1, increasing wear. Also, it would be beneficial to have a mA-~riql which absorbs liquid only upon the qrp1irA~ n of ples~ulc;, thus limiting absorption of moisture from, for eY-q-mp1e, a humid envii~nl"~nl when the foolwear product is not being worn. Thus, there is a need for a liquid retqining~ co",l"~.sion 15 moldable ColllpG~ foam mqtPriql that does not swell and which absorbs moisture only upon app1irq-tion of ~ for use as a footwear insole and/or as a shoe and boot liner.
Until the present i~venlion, there was no known polyul~lLa~le m~~eriq1 that, when ccr t,arvted with moi~hlre~ wicks it from the surface and locks it in place upon :~rp1ir, ~i~n of ~ SS~llc; to the mqt~riql The non-swelling absoll~"l capacity of the present invention is 20 another ~ul~lisillg and ~ ecl~ result of the novel col"~ûsilion of the present invention, providing results superior to the al~soll~lll m~~oriqlc of the prior art.
The novel composition of the polyul~ le foam of the present invention is also s~nrri.~ing and ~ l~t~ Methy1~nP11;p!~ -.yl diisocy~late is a non-hydl~philic prepolymer which, when incc.l~ulated into a foam, would be eYpcted to block off access of mQi~ re to 25 any incol~ldted superal)sull~"l polymers, and would thus be e~ ;t~ to create a foam which would not have liquid-locking capqt i1iti~s. An absol~.~l foam based on methylenediphenyl diisocyanate which illcol~l~tes surer~bso~l~e"l polymers was not knûwn in the art prior to the present invention, and thus its unique plu~,lies were also not a~ aled by the art.
W O 97/4S206 PCT~US97110216 Objects of the I~ on It is one object of the present invention to provide a hy~ophilic polyurelhalle foam that is based on the non-hydl~philic prepolymer methy1P..-Ari;~ ..yl diisocy~ulate which S comrri~es a superabsoll,elll polymer, and which absorbs fluid upon application of p,es~u~.
It is a further object of the present ",-/e.~Loil to provide an abso,~l~l cushioning footwear product comrri~e~ of a non-hy~philic polyulell.alle foam which, when used as in insole or liner in a foot covering, se~ves to absorb moisture produced by the feet and thereby keep moisture away from the feet of the wearer of the foot covering.
Another object of the invention is to provide an abs(slbe,ll, b,~
cushioning footwear product which does not absorb moisture unless p~s~ is applied to the surface of the absoll~l~l footwearproduct, and which contin~ously releases al~so,l,ed moisture by evaporation (i.e whether or not ~I~CS~ulc iS applied).
Summary of the I~ ~ion The present inv~ n is a dl-rahl~, breathable, liquid abso,l~lll, liquid locking,moldable composite m~~Pri~l comrri~ing a i,ul!st~, te and a polyu,~,ll,ane foam L"~ ed into or coated on the .s~bst~te, the polyw~ll,~le foam being made fmm a polyol, a non-llydl~hilic prepolymer, a s~e.dbsoll~l-l polymer and one or more su~f ~t~nt~.
The co",l)osile m~tt~.ri~l can further comrri~e an acrylic polymer to impart mcld~hility and co",~lcs.il-;lity c-h~r~ct~ri~ti~s to the m~tr.ri~l.
Detailed Description of the Invention A~l patents and pU~ ionc cited herein are hereby il~co,~,dted by ,~f~ ce.
25 In the event of a conflict in terminology, the present ~licclosl~re is controlling.
The composite m~t~ri~l of this invention is comI)ri~ed of an open cell, polyul~tha~e foam illlp~ P,-1 into or coated onto a woven or non-woven svl,~ e. The polyu~el~le foam is the reaction product of a methylP~ he~yl diisocyanale prepolymer and a polyol, s~ ~t~nt~ and optionally an acrylic polymer. The acrylic polymer, when 30 added, is added in an amount snfflcient to impart mol~ le chq~ teri~ti-~s to the foam. The composite mqtPrisl further col"~ises one or more superabsoll,cnl polymers that have either been mP~hqnitqlly ~t~~hP~ to the non-woven fabric or incorporated into the polywclha,~f foam. In a pl~f~lcd emb~imPnt, the ~u~c.dbsoll~nl polymer is incûl~ led into thepol~ulclllane; foam. The composite mqterisl can also opti~ nslly comprise a nP~AI~.J.~
S fiber finish which serves to ~i~pp~r~ce liquid to the interior of the foam and to impart surface structure to the col~,posile mqtP.risl The superabsoll~.d polymer-co.~ g polyulc~ e foam of the invention is p,~ d by mixing ~ogcll~f r one (1) part of a methylP-nP~ .hf ~.yl diisocyanate prepolymer and two (2) to six (6) parts of a polyol colllpone..ll. The polyol col~,pone.ll contains a polyether 10 polyol, surf~ctq-ntc, such as a plu~lene oxide/ethylene oxide block co~olymer such as Pluronic k62 (about 2-15% of polyol co~ on~n~ by weight, preferably about 10% byweight), a 10% ~q~leous solution of a propylene oxide/cthyl~.~ oxide block copolymer such as Pluronic F-88 (about 0.25-3% of polyol COIl~pOl~ by weight, plef~,dbly about 2% by weight), one or more superabsorbent polymers (0.25-2% of polyol co",pon~"l by weight, 15 preferably about 2% by weight) and, opti~nqlly~ an acrylic polymer (.25-10% of polyol col"~)on~,nl by weight, preferably about 3 % by weight). The acrylic polymer, when added, provides moldability to the fin;chP11 plUdUCI.
The prepolymer and polyol co...~e~ are cr~ f~ in t_e appropriate ~lq~thies and thoroughly mixed. A plcr~l~ d method of mixing utilizes a foam m~ hinP of 20 the type well-known in the art, with a mixing head rotating at bct~oen 2500 and 4000 rpm.
The ~ lulc is dischal~ed into a ~ b~ e, preferably a carded, airlaid non-woven mqtPIiql~
w_ich has been position~d on top of a flat release nlqtPriql, such as silicQnP cûated release paper (e.g. 92# Stay Flat k3 Liner, Terhnicote~lsiltech) Inc., ~;~ OH). The foam is sandwiched on top by another piece of the release n~qt~riql The non-woven ~ubsl ~. 'e can 25 be a rn-q-tP.riql such as 2.5 ounce/square foot Better Blend (Carlee Corporation, 1~1rlPigh, NJ). The papers Callylng the ~ sh~le travel ho.~lll~lly at a speed dct~ to be s~fficient to deposit an amount of the iso~ le/polyol mixture which will yield a ~.~h of the desired thicl~n~s~s~
The polymer is allowed to react with the polyol, yielding ca~bon dioxide and 30 a polyulc;lha~e, c, ..~.ng a foam il"pl~;n ~- 1 non-woven to form. The evolving gas is l..~
W O 97/45206 PCTrUS97/10216 s in the reacting ~ ~ and form the cells of the foam. As more carbon dioxide gas is ~,e~ ~, the cells enlarge and the react. nt mass eYp ~n~l~ pluJ)Gllionately, causing the foam to rise. At some point, the limitin~ reactant (iso~;yalldlG funrtir~nql prepolymer) is depleted and gas gen~ on halts, typically in 4 to 6 minutes. After about siY. . -i~.- les, the top and S bottom release papers are cQnti~ usly removed, exposing the co.~ os;le mqtP.riql The compositP~ mqtPriq1 is then moved into a forced . ~r convection oven ~'5i~ at 220~F to 275~F in order to finish cure the mq,t~iql. ~ liti~ nql reactions occur such as chain eYtencion and crocclinlrin~ to yield a "cured" three ~limPn~ionql network of a non-l.ydlu~Jhilic polymer foam. When cured, the product is Iyl ;~qlly, but not limited to, from one-eighth inch to one-10 ha1f inch in thir~nes~ After curing, the n~qtP.riql can be die cut to the desired shape andmolded. The reslllting mqt~.riql typically is capable of absu.l,ih~g from about five to about twenty times its weight in water.
The çhemi~ql re-q-~ti- n.c oc~-u. . ;.~ during polyule~ e foam mqmlf~ lre and contin~-o~s and discc,ll~il,uuus meth~s for such tnqn~f~~tllre are di~cussP~l more fully in 15 "Polyu,GIllalle Handbook, 2nd Edition" edited by Gunter Oertel, Hanser Pu~ chprs~ Mllnirh, (pp. 11-244) 1993, herein i. co,~.dted by ,~,f~ ce.
A pr~r~ d isocy~lale prepolymer is Flexible Products iso.;y~ale FP 100-A
polyulGIhan~ prepolymer derived from methyle~rA;~ F-~yl liiso.iy~u~lc. A p~f~ d polyol for use in the polyol coll.polle,~l is FP 100-B. Also pl~r~.rGd is FP 365-6 (Flexible Products, 20 M~riPtt~ GA). ~f~llcd sl~rf~ct~nt~ are Pluronic L-62 and Pluronic F-88 (BASF Corp., ChqrlottP, NC). A p~f~ d acrylic polymer for use in the ill~ lion is Rhoplex TR407 e.mulcion (Rohm & Haas Co, Phil~1elphi~, PA). ~fc..~d s~perqhso.l~.-l polymers are chqrs~ct~ ,d by being able to absorb from ahout 1000 to about 5000 pe.~nl by weight of ~qu~Pous sollltion~ and to hold such fluid under pl~S~ ,S of up to about 80 psi wilh.Jul 25 d~,~. al~.~g. Such .superPqbsoll~nl polymers include croc-c-linl~p~d polyacrylate polymer, starch grafted polyacrylate polymer, crosc-linlrP11 pop- Ccium polyacrylate/pol~,a.;lyldlllide, sodium salt of crosclinl~P~l polyacrylic acid polyalcohol graft copolymer, partial sodium salt of crosslin~e~
polyacrylic acid, crosc-linlr~P,~l polyvinyl pyrrolidQne, crosslinked sul~natcd polystyrene, crosclinkP~I polysulfoethyl(meth)acrylate, crosclin~d poly(2-ethylhexylacrylate), and 30 crolc.clink~ hyd~ly~d polyacryl~mitrilp. A p.~r~ ,d superabsoll~nl polymer for use in the mqtP.riql of the invention is AP80HS ~ abs~lbGnl polymer (Storl~h -usen, Inc., C~nsbor~"
NC).
In an embodiment in which the s1lrPr;~bso~bGlll polymer is ~co.~l.lled into the mqtP.riq1 of the invention by mPrhqnirq1 qtt~~hmPnt, the polymer is ~PnPr~q11y qtt~~hP~ to the S non-woven using a pl~ ul~,-3ellsilive cement or contact adhesive. The adhesive may be water born, solvent born, or hot melt. The qmount of adhesive applied will be ~lep~ -n on the amount of superabs~ll,enl polymer which is to be qtt ~h~7 and can be readily as~l~h~ed by those of oldinal~l skill in the art. A non-1;-~ ;n~ G~ Jle of such an adhesive is Super 77 spray adhesive (3M Co,~.~lion, St. Paul, MN). The foam to be used in this embodiment 10 does not contain superabsoll,c~l~ polymers. This foam is p.G~ d by the same method as the foam co.~ g supp~r~ql~soll~ ll polymers, except that water is ~ub,~;luled for the s~1rPr.q1-sl3.l,el~l polymer in the polyol colnronPnt The co.--l~s~ Pnq1~ of this invention can be fu~ther m~ifiP~ uti1i7ing a nP~1P.~u.-~ h:~g process that embeds and ~un.;lu,~,s fibers of a finish mqtPriq1 into the foam 15 mqtPriq1 This ne~A1~.~u,~h;.~g process can enhqnre the ~.rGl.~ ~ rhq~~P-ri~tirs of the product and provide the product with a finished sl~rf. ~e, which can be benPfir;q1 for ~sth~tic as well as funrtin q1 reasons. When present, a fiber finish mqtPriq1 can aid in passing fluids to be absorbed into the und~.ly,ng foam matrix. The fibers of the finish can be either hy~l)hilic or hyd~phobic, and serve to guide or draw fluids into the foam matrix leaving 20 a soft, dry surface. Non1;-..;~ ~llp'es of fibers which can be used in this finish of the present invention are acrylic, polyI,lop~lene, or polyester fibers, or a blend of these.
Example A polyul~ G foam was pl~l)~d by mixing tc.~ er one (l) part of an 25 isocyanate FP lO0-A prepolymer and four (4) parts of a polyol co..~ r-~ The polyol con~ollcnl colll~lised polyol FP lO0-B, Pluronic Lr62 (10% by weight), a 10% aqueous solution of Pluronic F-88 (2% by weight), Rhoplex TR 407 (3% by weight) and super~l soll~llt polymer AP80HS (2% by weight). The two colllpon~.~ were brought~gethPr in a mixing head at about 4000 rpm. The lllh~lul~ was allowed to discl~e into a 30 carded, airlaid non-woven on top of a ~i1iconP coated release paper and sandwiched on top W O 97/45206 PCTrUS97/10216 by another silicone coated release paper. The papers traveled hol~nl~lly at 4 feet per minute, yielding a thir~n-Pss of one-quarter inch in the product.
During the next four to six mim~tes~ the polymer reacted with the polyol causing a foam ul~pl~nated non-woven to form. After six ...i...~es the top and bottom S release papers were cc-ntin--ou~ly removed from the top surface, C;A~)OSmg the mqtPri~l. The product was then carried by a moving belt into a forced air convection oven m5;..1;. IrA at 220~F for the ~u,~ose of finish curing. The res~lting m~Priql was an open cell foam, A non-woven, white in color, one-quarter inch thick, that was wettable when was applied to the surface in contact with moisture.
10 Field of the Invention This invention relates to a liquid locking, moldable, non-swelling, polyu~lhdllefoam i~lly~g~ eA into a non-woven fabric. More particularly, it relates to a durable, liquid abso.l~n~, non-swelling, col-~y~,ssion moldable composite mqtPriql ehat locks in fluids when su~je~l~d to pl~S~lc.
R~~ru~d of the Invention The problem of moisture collectin~ in shoes, boots, and other footwear has long been a problem in the footwear art. Moi~re released by the foot, if not wicked away, can cause discclllfoll, tt;ll~yel~llulc ~ n~es~ blisters, and fungus growth.
Typically, the moisture yl~ has been addressed by h~colyo,~ling a mni~lre-wiC~ing liner in the footwear product. Such liners are often made from textile and nonwoven mqttqriq1~ or a combillali~n of both.
Foam footwear insoles are well-known in the art, typically being co~ ,ised of a ~ te conlplisi"g a liner mqfPri~l as a top layer, a foam or other cushioning mqtçri~l, 25 and a slirr~ner un-le~ the foam and liner layers. The foams are typically polyul~ e or polyethylene foams. Current footwear insoles foams are resilient and provide a shock-c(~ ents of the insoles of the prior art do not provide for wicking of moisture away from the foot and subse~luenl locking of the moisture in the insole.
The use of foams made from hyd~llilic polymers as cu~hinl ing and absorptive insoles for footwear is one possible solution to the above problem. However, S footwear insoles co..~ d of foams made from hyd~hilic polymers have ~ignifi(~nt disadvq-nt-a~es. Swelling occurs upon liquid absorption in almost all polymeric foam compositions made from hydlu~llilic polymers. In these foams, i.e., those which use a hydlophilic polymer, absol~Jtion takes place ~n the polymer, which 11IG1~;rU1~ swells. The swelling ~ fi~1res the thw~np~ss of the product, which is a pl~- n in the limited volume of lO a shoe cavity. Further, c1-~n~s in f1;~ nA;~ of the foam can cause stress on the junction of the foam with the other e1~ of the foolw~ mqtPriq1, increasing wear. Also, it would be beneficial to have a mA-~riql which absorbs liquid only upon the qrp1irA~ n of ples~ulc;, thus limiting absorption of moisture from, for eY-q-mp1e, a humid envii~nl"~nl when the foolwear product is not being worn. Thus, there is a need for a liquid retqining~ co",l"~.sion 15 moldable ColllpG~ foam mqtPriql that does not swell and which absorbs moisture only upon app1irq-tion of ~ for use as a footwear insole and/or as a shoe and boot liner.
Until the present i~venlion, there was no known polyul~lLa~le m~~eriq1 that, when ccr t,arvted with moi~hlre~ wicks it from the surface and locks it in place upon :~rp1ir, ~i~n of ~ SS~llc; to the mqt~riql The non-swelling absoll~"l capacity of the present invention is 20 another ~ul~lisillg and ~ ecl~ result of the novel col"~ûsilion of the present invention, providing results superior to the al~soll~lll m~~oriqlc of the prior art.
The novel composition of the polyul~ le foam of the present invention is also s~nrri.~ing and ~ l~t~ Methy1~nP11;p!~ -.yl diisocy~late is a non-hydl~philic prepolymer which, when incc.l~ulated into a foam, would be eYpcted to block off access of mQi~ re to 25 any incol~ldted superal)sull~"l polymers, and would thus be e~ ;t~ to create a foam which would not have liquid-locking capqt i1iti~s. An absol~.~l foam based on methylenediphenyl diisocyanate which illcol~l~tes surer~bso~l~e"l polymers was not knûwn in the art prior to the present invention, and thus its unique plu~,lies were also not a~ aled by the art.
W O 97/4S206 PCT~US97110216 Objects of the I~ on It is one object of the present invention to provide a hy~ophilic polyurelhalle foam that is based on the non-hydl~philic prepolymer methy1P..-Ari;~ ..yl diisocy~ulate which S comrri~es a superabsoll,elll polymer, and which absorbs fluid upon application of p,es~u~.
It is a further object of the present ",-/e.~Loil to provide an abso,~l~l cushioning footwear product comrri~e~ of a non-hy~philic polyulell.alle foam which, when used as in insole or liner in a foot covering, se~ves to absorb moisture produced by the feet and thereby keep moisture away from the feet of the wearer of the foot covering.
Another object of the invention is to provide an abs(slbe,ll, b,~
cushioning footwear product which does not absorb moisture unless p~s~ is applied to the surface of the absoll~l~l footwearproduct, and which contin~ously releases al~so,l,ed moisture by evaporation (i.e whether or not ~I~CS~ulc iS applied).
Summary of the I~ ~ion The present inv~ n is a dl-rahl~, breathable, liquid abso,l~lll, liquid locking,moldable composite m~~Pri~l comrri~ing a i,ul!st~, te and a polyu,~,ll,ane foam L"~ ed into or coated on the .s~bst~te, the polyw~ll,~le foam being made fmm a polyol, a non-llydl~hilic prepolymer, a s~e.dbsoll~l-l polymer and one or more su~f ~t~nt~.
The co",l)osile m~tt~.ri~l can further comrri~e an acrylic polymer to impart mcld~hility and co",~lcs.il-;lity c-h~r~ct~ri~ti~s to the m~tr.ri~l.
Detailed Description of the Invention A~l patents and pU~ ionc cited herein are hereby il~co,~,dted by ,~f~ ce.
25 In the event of a conflict in terminology, the present ~licclosl~re is controlling.
The composite m~t~ri~l of this invention is comI)ri~ed of an open cell, polyul~tha~e foam illlp~ P,-1 into or coated onto a woven or non-woven svl,~ e. The polyu~el~le foam is the reaction product of a methylP~ he~yl diisocyanale prepolymer and a polyol, s~ ~t~nt~ and optionally an acrylic polymer. The acrylic polymer, when 30 added, is added in an amount snfflcient to impart mol~ le chq~ teri~ti-~s to the foam. The composite mqtPrisl further col"~ises one or more superabsoll,cnl polymers that have either been mP~hqnitqlly ~t~~hP~ to the non-woven fabric or incorporated into the polywclha,~f foam. In a pl~f~lcd emb~imPnt, the ~u~c.dbsoll~nl polymer is incûl~ led into thepol~ulclllane; foam. The composite mqterisl can also opti~ nslly comprise a nP~AI~.J.~
S fiber finish which serves to ~i~pp~r~ce liquid to the interior of the foam and to impart surface structure to the col~,posile mqtP.risl The superabsoll~.d polymer-co.~ g polyulc~ e foam of the invention is p,~ d by mixing ~ogcll~f r one (1) part of a methylP-nP~ .hf ~.yl diisocyanate prepolymer and two (2) to six (6) parts of a polyol colllpone..ll. The polyol col~,pone.ll contains a polyether 10 polyol, surf~ctq-ntc, such as a plu~lene oxide/ethylene oxide block co~olymer such as Pluronic k62 (about 2-15% of polyol co~ on~n~ by weight, preferably about 10% byweight), a 10% ~q~leous solution of a propylene oxide/cthyl~.~ oxide block copolymer such as Pluronic F-88 (about 0.25-3% of polyol COIl~pOl~ by weight, plef~,dbly about 2% by weight), one or more superabsorbent polymers (0.25-2% of polyol co",pon~"l by weight, 15 preferably about 2% by weight) and, opti~nqlly~ an acrylic polymer (.25-10% of polyol col"~)on~,nl by weight, preferably about 3 % by weight). The acrylic polymer, when added, provides moldability to the fin;chP11 plUdUCI.
The prepolymer and polyol co...~e~ are cr~ f~ in t_e appropriate ~lq~thies and thoroughly mixed. A plcr~l~ d method of mixing utilizes a foam m~ hinP of 20 the type well-known in the art, with a mixing head rotating at bct~oen 2500 and 4000 rpm.
The ~ lulc is dischal~ed into a ~ b~ e, preferably a carded, airlaid non-woven mqtPIiql~
w_ich has been position~d on top of a flat release nlqtPriql, such as silicQnP cûated release paper (e.g. 92# Stay Flat k3 Liner, Terhnicote~lsiltech) Inc., ~;~ OH). The foam is sandwiched on top by another piece of the release n~qt~riql The non-woven ~ubsl ~. 'e can 25 be a rn-q-tP.riql such as 2.5 ounce/square foot Better Blend (Carlee Corporation, 1~1rlPigh, NJ). The papers Callylng the ~ sh~le travel ho.~lll~lly at a speed dct~ to be s~fficient to deposit an amount of the iso~ le/polyol mixture which will yield a ~.~h of the desired thicl~n~s~s~
The polymer is allowed to react with the polyol, yielding ca~bon dioxide and 30 a polyulc;lha~e, c, ..~.ng a foam il"pl~;n ~- 1 non-woven to form. The evolving gas is l..~
W O 97/45206 PCTrUS97/10216 s in the reacting ~ ~ and form the cells of the foam. As more carbon dioxide gas is ~,e~ ~, the cells enlarge and the react. nt mass eYp ~n~l~ pluJ)Gllionately, causing the foam to rise. At some point, the limitin~ reactant (iso~;yalldlG funrtir~nql prepolymer) is depleted and gas gen~ on halts, typically in 4 to 6 minutes. After about siY. . -i~.- les, the top and S bottom release papers are cQnti~ usly removed, exposing the co.~ os;le mqtP.riql The compositP~ mqtPriq1 is then moved into a forced . ~r convection oven ~'5i~ at 220~F to 275~F in order to finish cure the mq,t~iql. ~ liti~ nql reactions occur such as chain eYtencion and crocclinlrin~ to yield a "cured" three ~limPn~ionql network of a non-l.ydlu~Jhilic polymer foam. When cured, the product is Iyl ;~qlly, but not limited to, from one-eighth inch to one-10 ha1f inch in thir~nes~ After curing, the n~qtP.riql can be die cut to the desired shape andmolded. The reslllting mqt~.riql typically is capable of absu.l,ih~g from about five to about twenty times its weight in water.
The çhemi~ql re-q-~ti- n.c oc~-u. . ;.~ during polyule~ e foam mqmlf~ lre and contin~-o~s and discc,ll~il,uuus meth~s for such tnqn~f~~tllre are di~cussP~l more fully in 15 "Polyu,GIllalle Handbook, 2nd Edition" edited by Gunter Oertel, Hanser Pu~ chprs~ Mllnirh, (pp. 11-244) 1993, herein i. co,~.dted by ,~,f~ ce.
A pr~r~ d isocy~lale prepolymer is Flexible Products iso.;y~ale FP 100-A
polyulGIhan~ prepolymer derived from methyle~rA;~ F-~yl liiso.iy~u~lc. A p~f~ d polyol for use in the polyol coll.polle,~l is FP 100-B. Also pl~r~.rGd is FP 365-6 (Flexible Products, 20 M~riPtt~ GA). ~f~llcd sl~rf~ct~nt~ are Pluronic L-62 and Pluronic F-88 (BASF Corp., ChqrlottP, NC). A p~f~ d acrylic polymer for use in the ill~ lion is Rhoplex TR407 e.mulcion (Rohm & Haas Co, Phil~1elphi~, PA). ~fc..~d s~perqhso.l~.-l polymers are chqrs~ct~ ,d by being able to absorb from ahout 1000 to about 5000 pe.~nl by weight of ~qu~Pous sollltion~ and to hold such fluid under pl~S~ ,S of up to about 80 psi wilh.Jul 25 d~,~. al~.~g. Such .superPqbsoll~nl polymers include croc-c-linl~p~d polyacrylate polymer, starch grafted polyacrylate polymer, crosc-linlrP11 pop- Ccium polyacrylate/pol~,a.;lyldlllide, sodium salt of crosclinl~P~l polyacrylic acid polyalcohol graft copolymer, partial sodium salt of crosslin~e~
polyacrylic acid, crosc-linlr~P,~l polyvinyl pyrrolidQne, crosslinked sul~natcd polystyrene, crosclinkP~I polysulfoethyl(meth)acrylate, crosclin~d poly(2-ethylhexylacrylate), and 30 crolc.clink~ hyd~ly~d polyacryl~mitrilp. A p.~r~ ,d superabsoll~nl polymer for use in the mqtP.riql of the invention is AP80HS ~ abs~lbGnl polymer (Storl~h -usen, Inc., C~nsbor~"
NC).
In an embodiment in which the s1lrPr;~bso~bGlll polymer is ~co.~l.lled into the mqtP.riq1 of the invention by mPrhqnirq1 qtt~~hmPnt, the polymer is ~PnPr~q11y qtt~~hP~ to the S non-woven using a pl~ ul~,-3ellsilive cement or contact adhesive. The adhesive may be water born, solvent born, or hot melt. The qmount of adhesive applied will be ~lep~ -n on the amount of superabs~ll,enl polymer which is to be qtt ~h~7 and can be readily as~l~h~ed by those of oldinal~l skill in the art. A non-1;-~ ;n~ G~ Jle of such an adhesive is Super 77 spray adhesive (3M Co,~.~lion, St. Paul, MN). The foam to be used in this embodiment 10 does not contain superabsoll,c~l~ polymers. This foam is p.G~ d by the same method as the foam co.~ g supp~r~ql~soll~ ll polymers, except that water is ~ub,~;luled for the s~1rPr.q1-sl3.l,el~l polymer in the polyol colnronPnt The co.--l~s~ Pnq1~ of this invention can be fu~ther m~ifiP~ uti1i7ing a nP~1P.~u.-~ h:~g process that embeds and ~un.;lu,~,s fibers of a finish mqtPriq1 into the foam 15 mqtPriq1 This ne~A1~.~u,~h;.~g process can enhqnre the ~.rGl.~ ~ rhq~~P-ri~tirs of the product and provide the product with a finished sl~rf. ~e, which can be benPfir;q1 for ~sth~tic as well as funrtin q1 reasons. When present, a fiber finish mqtPriq1 can aid in passing fluids to be absorbed into the und~.ly,ng foam matrix. The fibers of the finish can be either hy~l)hilic or hyd~phobic, and serve to guide or draw fluids into the foam matrix leaving 20 a soft, dry surface. Non1;-..;~ ~llp'es of fibers which can be used in this finish of the present invention are acrylic, polyI,lop~lene, or polyester fibers, or a blend of these.
Example A polyul~ G foam was pl~l)~d by mixing tc.~ er one (l) part of an 25 isocyanate FP lO0-A prepolymer and four (4) parts of a polyol co..~ r-~ The polyol con~ollcnl colll~lised polyol FP lO0-B, Pluronic Lr62 (10% by weight), a 10% aqueous solution of Pluronic F-88 (2% by weight), Rhoplex TR 407 (3% by weight) and super~l soll~llt polymer AP80HS (2% by weight). The two colllpon~.~ were brought~gethPr in a mixing head at about 4000 rpm. The lllh~lul~ was allowed to discl~e into a 30 carded, airlaid non-woven on top of a ~i1iconP coated release paper and sandwiched on top W O 97/45206 PCTrUS97/10216 by another silicone coated release paper. The papers traveled hol~nl~lly at 4 feet per minute, yielding a thir~n-Pss of one-quarter inch in the product.
During the next four to six mim~tes~ the polymer reacted with the polyol causing a foam ul~pl~nated non-woven to form. After six ...i...~es the top and bottom S release papers were cc-ntin--ou~ly removed from the top surface, C;A~)OSmg the mqtPri~l. The product was then carried by a moving belt into a forced air convection oven m5;..1;. IrA at 220~F for the ~u,~ose of finish curing. The res~lting m~Priql was an open cell foam, A non-woven, white in color, one-quarter inch thick, that was wettable when was applied to the surface in contact with moisture.
Claims (9)
1. A durable, breathable, liquid absorbent, liquid locking, moldable composite material comprising:
a substrate;
a polyurethane foam impregnated into or coated on said substrate, wherein said polyurethane foam comprises a polyol, a non-hydrophilic prepolymer, a superabsorbent polymer and one or more surfactants.
a substrate;
a polyurethane foam impregnated into or coated on said substrate, wherein said polyurethane foam comprises a polyol, a non-hydrophilic prepolymer, a superabsorbent polymer and one or more surfactants.
2. The material of claim 1 wherein said polyurethane foam is formed by reaction of a non-hydrophilic isocyanate polymer and a polyol in a ratio in the range form 1:1 to about 6:1.
3. The material of claim 3 wherein said foam is comprised of Flexible Products FP100-A isocyanate and a member selected from the group consisting of Flexible Products FP 100-B polyol and Flexible Products FP 365-6 polyol.
4. The material of claim 1 wherein said polyurethane foam further comprises an acrylic polymer in an amount sufficient to impart moldability to said material.
5. The material of claim 1 wherein said material is capable of absorbing from five to twenty times its weight in water.
6. The material of claim 5 where in said material is compression moldable using standard equipment.
7. The material of claim 1 wherein said material is fiber needlepunched using an acrylic, polyester or polypropylene fiber blend that is hydrophobic or hydrophilic.
8. The material of claim 1 wherein said superabsorbent polymer is impregnated in said non-woven carded material.
9. The material of claim 1 wherein said superabsorbent polymer is a component of said polyurethane foam.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1889896P | 1996-05-30 | 1996-05-30 | |
| US60/018,898 | 1996-05-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2257170A1 true CA2257170A1 (en) | 1997-12-04 |
Family
ID=21790326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2257170 Abandoned CA2257170A1 (en) | 1996-05-30 | 1997-05-30 | Absorbent footwear material |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0902730A1 (en) |
| JP (1) | JP2000511952A (en) |
| AU (1) | AU3234397A (en) |
| CA (1) | CA2257170A1 (en) |
| WO (1) | WO1997045206A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001079341A1 (en) * | 2000-04-17 | 2001-10-25 | T H C Pty Ltd | Humidity sensitive composition |
| WO2013056401A1 (en) * | 2011-10-21 | 2013-04-25 | Bayer Materialscience Ag | Process for the production of coated textiles |
| CN109096464B (en) * | 2018-07-05 | 2020-12-18 | 山东一诺威聚氨酯股份有限公司 | Breathable insole and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8927636D0 (en) * | 1989-12-06 | 1990-02-07 | Purification Prod | Improvements in the production of particulate solid-bearing air-permeable sheet materials |
-
1997
- 1997-05-30 JP JP09543093A patent/JP2000511952A/en active Pending
- 1997-05-30 WO PCT/US1997/010216 patent/WO1997045206A1/en not_active Application Discontinuation
- 1997-05-30 AU AU32343/97A patent/AU3234397A/en not_active Abandoned
- 1997-05-30 CA CA 2257170 patent/CA2257170A1/en not_active Abandoned
- 1997-05-30 EP EP97928026A patent/EP0902730A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000511952A (en) | 2000-09-12 |
| WO1997045206A1 (en) | 1997-12-04 |
| EP0902730A1 (en) | 1999-03-24 |
| AU3234397A (en) | 1998-01-05 |
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