ZA200703711B - Methods and materials for skin care - Google Patents

Description

METHODS AND MATERIALS FOR SKIN CARE

The present invention relates to a cosmetic method for minimizing, preventing and removing wrinkles and providing for smoother and more robust skin surfaces, and to the use of materials incorporating water-insoluble copper compounds for minimizing, preventing and removing wrinkles and providing for smoother and more robust skin surfaces and providing for smoother and more robust skin surfaces. ;

More particularly the present invention relates to a cosmetic method for minimizing, preventing and removing wrinkles and providing for smoother and more robust skin surfaces comprising applying a material incorporating water-insoluble copper compounds which release Cu’ ions, Cu™ ions or combinations thereof upon contact with a fluid to a body surface tc Je treated.

The invention also relates to the use of water-insoluble copper compounds which release Cu’ ions, Cu'’ ions or combinations thereof upon contact with a fluid for the manufacture of a material such as a fabric or an extruded film, filament or sheath to be brought into contact wit: a body surtace for preventing, minimizing and removing wrinkies and providing for smoother and more robust skin surfaces

The sheath or extruded film can be oi the new types of a monolithic layer with moisture removal properties or micro pu: gs.

In addition the present invention relates to the use of a polymeric film having microscopic water insoluble particles of ionic copper oxides in powdered form, embedded directly therein with a portion of said particles being exposed and protruding from surfaces thereof, which particles release Cu’ ions, Cu™ ions or combinations thereof upon contact with a fluid for the manufacture of a material for preventing, minimizing and removing wiinkles and providing for smoother and more robust skin surfaces.

Similarly, the present invention relales to the use of fibers incorporating water-insoluble copper compounds which release Cu’ ions, Cu™ ions or combinations thereof upon contact with a fiuid for the manufacture of a material for preventing, minimizing and removing w: inkles aria providing for smoother and more robust skin surfaces.

In preferred embodiments of the present invention, as described hereinafter, said fibers are polymeric fibers having said compounds incorporated therein and protruding from the surfaces thereof.

In other preferred embodiments of the present invention, as described hereinafter, said fibers are coated with aid copper compounds ;

In further preferred embodimenis of the present invention said material is formed from a polymeric component selected from the group consisting of a polyamide, a polyester, an acrylic and a polyalkylene, which would also include such materials as polypropylene, polyurethane, polyolefin, polyethylene, and other hydrophilic and hydrophobic polymers said material being in the form of a fiber, a yarn, or a sheet.

As will be described hereinafte.: with reference to the examples and the accompanying figures, it has now been surprisingly discovered that materials incorporating water-insoluble copper compounds which release Cu” ions, Cu’ ions or combinations therecf upon contact w:in a fiuid car be used for tne manufacture of a fabric, a film, a filament or a shea to be brougnt into contact with a body surface for the cosmetic use of preventing, minimizing and removing wrinkles and providing for smoother and more robust skin surfaces

More specifically, it has now been surprisingly found that the materials of the present invention are effective in preventing, minimizing and removing wrinkles and providing for smoother and more robust skin surfaces.

There is available on the market a cream for topical application, which includes an organic copper peptide as a component thereof. As will be realized however, said cream is designed to penratrate the skin and the system in light of the linkage of the copper within an organic copper peptide, and said product therefore would not teach or suggest io a person: skilied in the art that water-insoluble copper compounds which reiease Cu” ions, C.' icns or cornbinations thereof upon contact with a fluid can be used for the mar: i’actur2 of a fabric, a film, a filament or a sheath to be brought into contact with a tody surface for the cosmetic use of preventing, minimizing and removing wrirkies and providing for smoother and more robust skin surfaces

In both WO 98/06508 and WC 87/06539 there are taught various aspects of a textile with a full or partial metal or metal oxide plating directly and securely bonded to the fibers thereof wherein rotal end mata! oxides, including copper, are bonded to said fibers.

More specifically, in WO 98/06509 there is provided a process comprising : the steps of. (a) providing a metallized textile, the metallized textile comprising: (i) a textile including fibers selected from the aroup consisting of natural fibers, synthetic cellulosic fibers, regenerated fibers, ac:yiic fibers, poiyolefin fibers, polyurethane fibers, vinyl fibers, and blends thereof, and (i1) a plating including materials selected from the group consisting of metals and metal oxides, the metallized textile characterized in that the plating is bonded directly to the fibers: and (b) incorporating the metallized textile in ar: article of manufacture. in the context of said invention the term “textile” included fibers, whether natural (for example, cotton, silk, wor! anc linen) or synthetic yarns spun from : those fibers, and woven, knit, and nur-vevan tabrics made of those yarns. The scope of said invention inciuded ail natural fibers; and all synthetic fibers used in textile applications, including but not limited to synthetic cellulosic fibers (i.e., regenerated cellulose fibers such as rayon, and cellulose derivative fibers such as acetate fibers), regenerated protein fibers, acrylic fibers, polyolefin fibers, polyurethane fibers, and vinyl fibers, but exciuding nylon and polyester fibers, and blends thereof.

Said invention comprised applicaticn to the products of an adaptation of technology used in the electrolyses praung of plastics, particularly printed circuit boards made of plastic, with metals. See, for example, Encyclopedia of Polymer

Science and Engineering (Jacqueline |. Kroschwitz, editor), Wiley and Sons, 1987, vol. IX, pp 580-598. As appiied to textiles, this process included two steps. The first step was the activation of tne textile by precipitating catalytic noble metal nucleation sites on the textile. This was done by 7i-;t soaking the textile in a solution of a low- oxidation-state reductant cation, and ther soakirg the textile in a solution of noble metal cations, preferably a solution ¢: Pd++ cations, most preferably an acidic

PdCl, solution. The low-oxidation-state cation reduces the noble metal cations to the noble metals themselves, while reing oxidized to a higher oxidation state.

J

Preferably, the reductant cation is one that is soluble in both the initial low oxidation state and the final high oxidation state, for example Sn++, which is oxidized to

Sn++++, or Ti+++, which is oxidized to ~ i++++.

The second step was the reduction, in close proximity to the activated textile, of a metal cation whose reduction was catalyzed by a noble metal. The reducing agents used to reduce the cations typically were molecular species, for example, formaldehyde in the case of Cu++. Bacause the reducing agents were oxidized, the metal cations are termed “oxidant cations’ herein. The metallized textiles thus produced were characterized in that their metal plating was bonded directly to the textile fibers.

In WO 98/06508 there is desciibed and claimed a composition of matter comprising: (a) a textile including fibers selected from the group consisting of natural fibers, synthetic cellulosic fibers, regenerated protein fibers, acrylic fibers, polyolefin fibers, polyurethane fioers, vi vi fibers, and biends thereof; and (b) a plating including mate: als selected from the group consisting of metals and metal oxides; the composition of matter characterized in that said plating is bonded directly to said fibers.

Said publication also claims a composition of matter comprising: (a) a textile including fibers seizzted from the group consisting of natural fibers, synthetic cellulosic fibers, regenerated orotein fibers, acrylic fibers, polyolefin fibers, polyurethane fibers, vi::yl fibers, and blends thereof; and (b) a plurality of nucleation s'tas, each of said nucleation sites including at least one noble metal; the composition of matter characterized by catalyzing the reduction of at least one metallic cationic species to a reduced metal, thereby plating said fibers with said reduced metal.

In addition, said publication tea: 2s and cigims processes for producing said products.

A preferred process for prepa~rq a metallized textile according to said publication comprises the steps of:

a) selecting a textile, in a form selected from the group consisting of yarn and fabric, said textile including fibers s=.ected from the group consisting of natural fibers, synthetic cellulosic fibers, re.jenerated protein fibers, acrylic fibers, polyolefin fibers, polyurethane fibers, vinyl fibers, and blends thereof; b) soaking said textile in a :olution containing at least one reductant cationic species having at least two positive oxidation states, said at least one : cationic species being in a lower of said at least two positive oxidation states; c) soaking said textile in a solution containing at least one noble metal cationic species, thereby producing an activated textile; and : 4d) reducing at least one oxidant cationic species in a medium in contact with said activated textile, thereby producing a rnetallized textile.

Said publications, however, were imited to coated fibers and textiles prepared according to said processes cr the uses cescribed therein, however said publications did not teach or suggest tnat such coated fibers and textiles could be effective for manufacture of a material ‘or preventing, minimizing and removing wrinkles and providing for smoother and morz robust skin surfaces.

Similarly said publications did not teach or suggest the possibility of ‘incorporating cationic copper into a nulymeric slurry of a hydrophobic polymer whereby there are produced films znd fibers having microscopic particles of cationic copper encapsulated therein and protruding there from which have now also been surprisingly disccvered as being effective fer manufacture of material for preventing, minimizing and removing wrinkles and providing for smoother and more robust skin surfaces.

According to the description in USSN 10/240993, the teachings of which are incorporated herein by reference, it was discovered that by adding a small percentage of Cu++ in the form of water insoluble copper oxide particles to the slurry of a polymer to be formed, the resulting polymer possessed antimicrobial properties.

Furthermore it was surprisingly iscoverec and described therein that by adding copper oxide in particle form i-'o a polymeric slurry of such polymers as polyethylene, poiypropylere, polyester. arid similar hydrophobic or hydrophilic polymeric materials it is possible to ex!'ude fibers, yarns or sheets which possess both antimicrobial and antiviral properties which have a multiplicity of uses. Among the uses contemplated for the novel araimicrobial and aritiviral polymeric materials described in said specification was their use in a backing for a carpet, which could even be used in a hospital setting since it would not develop mold, smell, and would inactivate any viruses settling thereon; the use as a component of a molded non- woven product such as an air filter in & hospital or airplane or a mask which could be made air permeable or liquid permeable and be used to filter fluids flowing there through and to inactivate bacteria and viruses found in said fluids; formation into a continuous, flat, textured or stretchec “orm which could be used in articles of clothing such as stockings, socks, snirts or any article of clothing that would incorporate a hydrophobic polymeric fiber or yarn; formation of a short staple fiber which could be then used as is or blended with other fibers such as cotton, which : blended yarns could then be used for ©1= manufacture of a variety of both knit and woven products such as socks, sheets. zfc.; and use of such polymeric materials, manufactured in the form of a bi-2 worent yar ir which the core is one compound and the sheath arcund the core is a pclymer containing the water insoluble copper oxide particles creatng a yarn with a multitude of end uses in either a continuous, flat, textured, stret hed form or as a short staple. An example of said latter use would be the use of a polyethylene core with a polymeric sheath incorporating said water insoluble copp«=r oxide particles to form a yarn with an increased resistance to being cut or rir-ced while also being both antimicrobial and antiviral and having a multiplicity of use: inciuding in the food preparation industry.

Said material was described :s being made from almost any synthetic polymer, which will allow the introducucn of an cationic, copper oxide particles into its liquid siurry state. Examples ot some materials are polyamides (nylon), polyester, acrylic, and polyalkylenes such as polysthvlene and polypropylene,

When the copper oxide dust is ground icwn to fine powder, e.g., a size of between 1 and 10 microns and introduced in: re slurry iri small quantities, e. g., in an amount of between 0.25 ard 10% of tr. 1¢'v ner weight, in a master batch as is the accepted practice for manuracturing esirruced fibers and films it was found that the subsequent product produced from rus slurry exhibited both antimicrobial and antiviral properties.

Unlike the fibers described, e. 4. in WO 98/06508 and WO 98/065089, in which the fibers are coated on the uiside, in said product the polymer has microscopic water insoluble particles ct < atioric cobper oxide encapsulated therein with a portion of said particles being exsused and protruding from surfaces thereof.

These exposed particles which protrud: from the surface of the polymeric material have been shown to be active, as demonstrated by the tests set forth in said * specification, and the teachings thereof as they are relevant to the present invention are incorporated herein by reference.

Said US specification, however also did not teach or suggest that the polymeric materials described therein ar effective for manufacture of a material for preventing, minimizing and removing w. i ikies and providing for smoother and more robust skin surfaces as described ana « <emiplified herein.

In general, the products of said zoecification and also products which can be used in the present invention are prod.” 4 as follows: 1. A slurry is preparea from arly wtiyimer, the chief raw material preferably being selected from a polyamide, a pclyalkyiene, a polyurethane and a polyester.

Combinations of more than one of sai: materials can aiso be used provided they are compatible or adjusted for comipuzobiity. The polymeric raw materials are usually in bead form and can be mono-component, bi-component or multi- component in nature. The beads are nzated to meiting at a temperature which preferably will range from about 120 to 130 *C. 2. At the hot mixing stage, befors ex‘rusion, a water insoluble powder of cationic copper oxide is added to the <iurry and allowed to spread through the heated slurry. The particulate size wi!" ne preferably between 1 and 10 microns, however can be larger when the film i: fiber thickness can accommodate larger particles. 3. The liquid slurry is then pushed with pressure through holes in a series of metal plates formed into a circle or oto: desired shape called a spinneret. As the slurry is pushed through the fine holes that are case together, they form single fibers or if allowed to contact one anotrg:, they form a film or sheath. The hot liquid fiber or film is pushea upward with coin =~ farming a continuous series of fibers or a circular sheet. The thickness of the *i' 5 or sheet is controlled by the size of the holes and speed at which the slurry is ri.shed through the holes and upward by the cooling air flow.

In WO 94/15463 there are descri?ad antimicrobial compositions comprising an inorganic particle with a first coating providing antimicrobial properties and a second coating providing a protective function wherein said first coating can be silver or copper or compounds of silver, copper and zinc and preferred are compounds containing silver and copper /1l) nxide. Said patent, however, is based on the complicated and expensive proce :s involving the coating of the metallic compositions with a secondary protective coating selected from silica, silicates, borosilicates, aluminosilicates, alumina, alummum phosphate, or mixtures thereof and in fact all the claims are directed to compositions having successive coatings including silica, hydrous alumina and dioctyi azelate.

In contradistinction, the present invenion is inter alia directed to the use of a polymeric material, having microscopic water insolutle particles of cationic copper oxide in powder form, wniur: release + ©" ercapswaied tnerein with a portion of said particles being exposed and pretruing from surtaces thereof, which is neither taught nor suggested by said publication and which has the advantage that the exposed Cu’ releasing water insoiuble particies which protrude from the polymeric material have been proven to be effective in preventing, minimizing and removing wrinkles and providing for smoother and more robust skin surfaces.

In EP 427858 there is described an zntibacterial composition characterized in that inorganic fine particles are woated with an aniibacterial metal and/or antibacterial metal compound and sai: r-atent does not teach or suggest a polymer that incorporates microscopic water insciubia particles of cationic copper oxide in powder form, which release Cu‘ enaosilated therein with a portion of said particles being exposed and pretruding om surfaces thereof.

In DE 4403016 there is described a nactericidal and fungicidal composition utilizing copper as oppose: to ionic © =:d said paient also does not teach or suggest a polymer that incorporates microscopic water insoluble particles of cationic copper oxide ir powder form. wi ich reiease Cu’ encapsulated therein with a portion of said particles being expose ; 21d protruding from surfaces thereof.

In JP-01 046465 there is described a condom releasing sterilizing ions utilizing metals selected from copper, silver, mercury and their alloys which metals have a sterilizing and sperm killing efic ct, wherein the metal is preferably finely powdered copper. While cooper salts such as copper chloride, copper sulfate and copper nitrate are also mentioned, as is known, these are water soluble salts which will dissolve and break down the polymer in which they are introduced. Similarly, while cuprous oxide is specifically mentioned. this is a Cu’ ionic form, and therefore said patent does not teach or sugges! tne use of exposed Cu" releasing water insoluble particles which protrude from the polymeric material and which have been proven to be effective in preventing, minimizing and removing wrinkles and providing for smoother and nore robust skin surfaces.

In JP-01 246204 there is described an antimicrobial molded article in which a mixture of a powdery copper compouna nd organic polysiloxane are dispersed into a thermoplastic molded article for the n-eparation of cioth, socks, etc. Said patent specifically states and teaches that rire! ions cannot be introduced by themselves into a polymer molecule and requires tn: inciusion of organopolysiioxane which is also intended to provide a connecting wath for the release of copper ions to the fiber surface. Thus, as will be realized said copper compound will be encapsulated and said patent does not teach or sugg::3t the use of exposed Cu’ releasing water insoluble copper oxide particles that prcit-ude frorn tne polymeric material.

In JP-03 113011 there is des hed a fiber naving good antifungal and hygienic action preferably for producing urderwear wherein said synthetic fiber contains copper or a copper comcound 1 combination with germanium or a compound thereof, however, said pat: t teaches and requires the presence of a major portion of germanium and the co2aoer compounds disclose therein are preferably metallic copper, cuprous io de wich is a monovalent Cu® compound and water soluble copper salts. Thus aid patent dces not teach or suggest the use of exposed Cu’ reieasing wz insoidtie copper oxide particles which protrude from the polymeric. material.

In EP 116865 there is described and ciaimed a polymer article containing zeolite particles at least part of wni: reiain at ‘east one metal ion having a bacterial property and thus said pate oes not teach or suggest the use of i) exposed Cu" releasing watar insoluble <opper oxide particles, by themselves and : in the absence of a zeolite, which partic:@s protrude from the polymeric material and which have been proven t.. be effeciiv: irc preventing, minimizing and removing wrinkles and providing for srnoother ari. more robust skin surfaces

In EP 253653 there is described and claimed a polymer containing amorphous aluminosilicate particles comprising an organic polymer and amorphous aluminosilicate solid particles or amore ous aluminosilicate solid particles treated with a coating agent, at ieast some of »ad amcrphous aluminosilicate solid particles holding metal ions having a bactericidal actions. Thus, said patent does not teach or suggest the use of exposed Cu” releasing water insoluble copper oxide particles, by themseives and in tne abserice of amorphous aluminosilicate particles, which exposed Cu’" releasing water insoluble copper oxide particles, protrude from the polymeric material ar ¢ which have been proven to be effective in preventing, minimizing and :emoving w.-ikies and providing for smoother and more robust skin surfaces.

Thus none of said publications ach or suggest the use of water-insoluble copper compounds which release Cu” iuns, Cu™ ions or combinations thereof upon contact with a fluid for the manufactu:= of a fabric or an extruded film, filament or sheath to be brought in contact with a oudy surface for preventing, minimizing and removing wrinkles and providing for smasher and more robust skin surfaces.

Thus, one preferred aspect of t= present invention relates to the use of fibers incorporating water-insoluble cr.coer cornpounds which release Cu’ ions,

Cu*" ions or combinations thereof upor contact with a fluid for manufacture of a material for preventing, minimizing =nd temeoving wrinkles and providing for smoother and more robust skin surface:

In preferred embodiments of <=wi aspect of the invention, said material is formed of a fabric material or a substir: = incorporating ficers treated with a cationic species of copper and ircorporating ate insoluble copper compounds which release Cu” ions, Cu’” ions or combiriz 1s thereof upon contact with a fluid.

It is to be noted that said fibers ». substrate can be made of a hydrophilic or a hydrophobic polymeric m.:teriai.

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In preferred embodiments of sa 1 first aspect cf the present invention, said fibers are polymeric fibers having ::d ccmpounds incorporated therein and protruding from the surfaces thereof in other preferred errbodiments 7 said aspect of the present invention said fibers are coated with said copper comp:-unds.

A second preferred aspect of the present invention relates to the use of a polymeric film having microscopic wate: insoluble particles of ionic copper oxides in powdered form, embedded directly th..r2in with a portion of said particles being exposed and protruding from surfaces irereof, which particles release Cu’ ions,

Cu” ions or combinations thereot upor. contect with a fluid for the manufacture of a material for preventing, rminimizing ard removing wrinkles and providing for smoother and more robust skin surfaces

A third preferred aspect of the present invention relates to the use of fibers incorporating water-insolubie copper cc ri naunds which release Cu’ ions, Cu®* ions or combinations thereof upon contact «Fh « via ‘or tive manufacture articles of clothing to be worn fer preventing, mar: eing an. removing wrinkies and providing for smoother and more robust skin surfaces.

Also in this third aspect of the j.izsent invention said fibers are preferably polymeric fibers having said compounds: incorporated therein and protruding from the surfaces thereof or said 1ibers are coaled with said copper compounds

A fourth preferred aspect of the present invention relates to the use of a polymeric fitra having microscopic wate * 1:sciubie: parucies of ionic cooper oxides in powdered form, embedded directly thwsin ain a portion of saia particles being exposed and protruding frum surface: hereof. which particles release Cu’ ions,

Cu” ions or combinations thereof upar —ontzict with a fluid for the manufacture of a tubular sheath for removaile position.ag cn the neck of a user to be worn for preventing, minimizing and removing wai ikie:s and providing for smoother and more robust skin surfaces.

A fitth preferred aspect of the | cert veinticn relates to the use of fibers incorporating water-insoluble copper c:imncui:ds which release Cu’ ions, Cu™ ions or combinations thereof upun contac: . ih a “hid for “he manufacture of a tubular sheath for removable positaning on r- nex Of a user to be worn for preventing,

minimizing and removing wrinkles and aroviding for smoother and more robust skin surfaces.

Also in this fifth aspsct of the preserit invention said fibers are preferably polymeric fibers having saicl compounds incorporated therein and protruding from the surfaces thereof or said fibers are coated with said copper compounds.

A sixth preferred aspect of the present invention relates to the use of fibers incorporating water-insoluble copper ccmpounds which release Cu® ions, Cu®* ions : or combinations thereof upon contact v ith a fluid for the manufacture of a fabric for preventing, minimizing and removing wrinkles ancl providing for smoother and more robust skin surfaces.

Preferably said fabric can be used in a pi:low case, a cover, a sheet or any textile article with which body surfaces prone to wrinkling can come in contact.

A seventh preferred aspect of ithe present invention relates to the use of fibers incorporating water-insoluble co.uper compounds which release Cu’ ions,

Cu" ions or combinations thereof uot © coma with a fluid for the manufacture of socks for preventing, minirnizing ana reroving wrinkles and providing for smoother and more robust skin surfaces.

An eighth preferred aspect of ine present invention relates to the use of fibers incorporating water-insoluble copper compounds which release Cu’ ions,

Cu" ions or combinations thereof upon contact with a fluid for the manufacture of a terry cloth material for preventing, mini izing and rernoving wrinkles and providing for smoother and more robust skin suff &s.

Similarly in preferred embodiments of the present invention, said fabric can be in the form of a scarf to be worn around the neck and to tubular sheath for removable positioning on the neck ¢i a user tw be worn for preventing, minimizing and removing wrinkles and providing 10: smoother and more robust skin surfaces.

In further preferred embodiments of the present invention, said fabric can be in the form of an at least pa:tiai face me ic.

Since there are people who ae sensitive with regard to the wrinkled appearance of their hands said fabric can also b2 in the form of gloves to be cosmetically worn for preventing, minimizing anc rerroving wrinkles and providing for smoother and more robust skin surfaces on hand surfaces.

Also in these aspecis of the presen: invention said fibers are preferably polymeric fibers having said compouna: incorperated therein and protruding from the surfaces thereof cr said fibers are ccated with saic copper compounds.

In another aspect of the present invention there is now provided a cosmetic method for preventing, minimizing and removing wrinkles and providing for smoother and more robust skin surfaces on skin surfaces comprising applying thereto a polymeric material formed from a polymeric component selected from the group consisting of a polyamide, a po.yester. an acrylic and a polyalkylene, said material being in the form of a fiber, a yarn, a sheath, a filament, or a sheet, and having microscopic water insoluble pariicles of ionic copper oxides in powdered form, embedded directly therein with a port.on of said particles being exposed and protruding from surfaces thereof, which particles release Cu’ ions, Cu® ions or combinations thereof upon contact with a fiuid.

In a first group of preferred embodiments of the present invention said material is a faoric having tioers incu uo ati wate nscukie copper compounds which release Cu’ ions, Cu’ ions or seritnalions therens upon contact with a fluid.

In a second group of preferred embodiments said material is a polymeric film having microscopic water insoluble pa ticles of ionic copper oxides in powdered form, embedded directly therein with a sortion of said particles being exposed and protruding from surfaces trereof, whici: particles release Cu’ ions, Cu®™ ions or combinations thereof upon contact with a fluid.

In a third group of preferred eincodimeris of the preserit invention said material is a polymeric fiber having micioscopic water insoluble particles of ionic copper oxides in powdered form, embeaded a.rectly therein with a portion of said particles being exposed ana orotruqiing irom surfaces thereof, which particles release Cu’ ions, Cu" ions or combinati.iis thereof upor: contact with a fluid.

In a fourth group of preferred macciments of ihe present invention said material is a polymeric filamant naving ricro-conic water insoluble particies of ionic copper oxides in powdered form, emb videa directly therein with & portion of said particles being exposed and grotruding frum surfaces thereof, which particles release Cu’ ions, Cu™ ions or combiratens thereat upon contact with: a fluid.

In a fifth group of preferred emdadiments cf the present invention said material is a polymeric sheath having n croscopic water insoluble particles of ionic copper oxides in powdered ‘orm, ember dea directly therein with a portion of said particles being exposed ard protruding frem surfaces thereof, which particles release Cu’ ions, Cu’ ions or combinat:ons thereof upon contact with a fluid.

In a sixth group of preferred embodiments of the present invention, said material is a polymeric film having microscopic water insoluble particles of ionic copper oxides in powdered yorm, einbeaaec directly therein with a portion of said particles being exposed and protruding frum surfaces thereof, which particles release Cu+ ions, Cu++ ions or combinations thereof upon contact with a fluid wherein said film has the abiiily to dispe-ue liquid thrcugh osmosis.

In a seventh group of preferred einbodanents ct the present invention, said material is a polymeric film having microscopic water insoluble particles of ionic copper oxides in powdered foi, embedded directly therein with a portion of said particles being exposad ad | rutruding fiom surfaces thereof, which particles release Cu+ ions, Cut - iors Or g combination thereof upon contact with a fluid wherein said film his micro pores perforated throughout to allow for the escape of excess liquids

As stated above, based on the surprising discovery of the present invention that a material incorporating water-insoiuble copper cusnpounds which release Cu” ions, Cu’ ions or combinatons thereof Lipo contact witn a fluid. can be used ina cosmetic method for preventing, minimizing and removing wrinkles and providing for smoother arid more robust skin surfaces, many articles of manufacture can be prepared for cosmetic use for achieving {nis nighiy desirable result.

The polymeric materials for use n the present invention can be produced by preparing a slurry of a polyrer selected itor the: groupe consisting of a polyamide, a polyester, an acrylic and a polyalkylene. and inixiures thereof, introaucing a powder consisting essentially of water insoluisi= nat-omic copper oxides and dispersing the same in said slurry and tren extrudic, ssid slurry to form a polymeric material wherein water insoluble covper oxide nattiies tnat release Cu” are encapsulated therein with a portion of s&'d particles ang exposed and protruding from surfaces thereof, which polymeric material is the ~ formed itu a fiber, a yarn or a sheet to be

” manufactured into a fabric suitable to be brought in contact with a body surface for preventing, minimizing and removing wrinkles and providing for smoother and more robust skin surfaces.

In US Patent 6,124,221 there is described and claimed an article of clothing having antibacterial, antifungal, and ariiyeast properties, comprising at least a panel of a metallized textile, the textile including fibers selected from the group consisting of natural fibers, synthetic cel.u:osic fibers, regenerated protein fibers, acrylic fibers, polyolefin fibers, pclyurettiane fibers, vinyi fibers, and blends thereof, and having a plating including an antibacieriai, antifungal and antiyeast effective amount of at least one oxidant cationic species of copper.

In said specification there was described that said article of clothing was effective against Tinea Peclis, against Casivida Aivicans, against Thrush and against bacteria causing foot odor, seiecteu fiom the group of brevubacterium, acinetobacter, micrococcus and combiric iuons thersof, hov.ever said patent did not teach or suggest that such an ariicle of hiv rp ware intended for use or would be effective in the treatment of cpen wou us sch as sores, cold sores, cutaneous openings, ulcerations, lesions, abrasioris anid burns.

In WO 01/81671 there is described tiat textile iabrics incorporating fibers coated with a cationic form: of copper zie also effective for the inactivation of antibiotic resistant strains of bacteria aric said cationic species of copper preferably comprises Cu" ions, however, aiso in is specification, the textile fabrics were described for use in treating a hospital environment to prevent tne spread of infection by the inactivation of such peacieria excreted by an infected patient and said specification did not teacn or suguest that an article of clothing formed from such a textile fabric would ve effective ior preventing rinimizing ana removing wrinkles and providing for srnoother and roe robust skin surfaces.

In WO 01,/74166 there is describ-d and claimed the use of particles which release Cu” for the preparation of :. ¢o'wrenc material having microscopic particles which release Cu’ encapsuls =d therein with a portion of said particles being exposed and protrudin 3 from suri ces thereof, said polymeric material being effective to inhibit HIV-1 prciiferatior. i :..eve: said publication was limited to the teaching of the use of such rolymeric m=t=rizls for the preparation of condoms and g8 possibly gloves and the irventor thar» f dd pot realize at said time and said publication does not teach or sugges! th= present inventive concept of providing an article of clothing which wo d be effet: « tor preventing, minimizing and removing wrinkles and providing for simoother anc 11:are robust skin surfaces.

In US Patent 5848592, US Pater: 549.2882 , French patent 2764518, British

Patent 1382820 and US Paient 5217624 there are variously disclosed air or water filters comprising copper metal, copg.:: oxides, chloride, carbonate and sulfate against noxious vapors and gases and ayairoi bactena and viruses. In the case of

British Patent 1382820 a gas filter is disclosed incorporating active carbon and/or an oxide or oxides of one ur more meizis of a hugh molecular weight in order to physically block and prevent the passage of bacteria. In the case of US patent 5215626 a water filter is disclosed incorpo:ating a mixture of a permanganate compound, a silver compound and « .valer-soiuble copper compound such as copper chioride or copper si ifate.

None of said references however, teach or suggest the use of fibers incorporating water-insoiuble copper coi pounds which release Cu’ ions, Cu** ions or combinations thereof upon contact wit a fluid, for the manufacture of a fabric to be brought in contact with a boay surfa. for preventing, minimizing and removing wrinkles and providing for smoother ani riace robust skin surfaces.

DATABASE WP! Section Ch, VW eek 193037 Derwent Publications Ltd,

London, GB; Class BO4, An 1390-234808 XP002247181 & JP 02 161954 and

DATABASE WPI Section Ch, Week 190821 Derwent Publications Ltd,. London,

GB; Class A88, An 1988-145060 XP00:2 47182 & JP 63 1088007 relate to hollow porous fibres ano especiaiv JP 831048007 discioses treating body fluids with cellulose bound copper ammcnium however iether of said references teach or suggest the use of fibers incorporating water-insuinte copper compounds which release Cu’ ions, Cu" ions or combins tis thereot upon contact with a fluid, for the manufacture of a fabri: to be tvreaunt in cortac! with a body surface for preventing, minimizing and removing wrinkies and providing for smoother and more robust skin surfaces.

As stated hereinbefcie WO 01/7456 teaches and claims an antimicrobiaf and antiviral polymeric material, havire micrascopic particles which release Cy™

V7 encapsulated therein and protruding fren surfaces thereof but does not teach or suggest the method of the present inveriic Simiiarly WO 01/81671 teaches and claims a method for combating and p' :verting rosocomial infections, comprising providing to health care facilities text:!-: fabrics incorporating fibers coated with a cationic form of copper, for use in paient contact and care, wherein said textile fabric is effective for the inactivation of antibiotic resistant strains of bacteria and also does not teach or suggest the use of fibers incorporating water-insoluble copper compounds which rzliease Cu’ iris, Cu* ions or combinations thereof upon contact with a fluid, for the manufacture of a fabric to be brought in contact with a body surface for preventing, minimizirg and removing wrinkles and providing for smoother and mare robust sxin surfaces.

Thus, none of the above publications teach or suggest the subject matter of the present invention. : In the method of the uresent inve on he cationic species of copper must be exposed to a liquid medium 0 allow in “tome dispe so into the medivm whether said medium is perspiration which acts as @ carrier for said atomic dispersion, or a liquid or surfactant which is added to th: fivers or fabric to facilitate the transfer of the ions to the skin surface 15 be treated: in order to form a cosmetic maleral of the present invention for preventing, minimizing and removing wrinkles and providing for smoother and more robust skin surfaces, one would preferably take fib='s having ionic copper selected from the group consisting of Cu” and Cu™ ions ad wiclude them in a substrate. In a woven substrate, the fibers would be blended w:iri any other fiber and woven or knit into a substrate. In a non-woven configuration: fe fibers wouid be blended to form a thin layer. In both cases, a numver of layers could preferably be placed one on top of the other to form a pad.

The ionic copper used in the methoa of the present invention is prepared in a manner similar to that described in «: eerlier specications referenced above with slight modifications as described f= ainafter and is obtained through a redox reaction either on a substrata or alone i tis: hquid. The method of production is an adaptation of technology as used in the eleclioless plating of plastics, particularly printed circuit boards made of plastic, -+.* metals See, for example, Encyclopedia of Polymer Science and Engineering (.lacgualine |. Kroschwitz, editor), Wiley and

Sons, 1987, vol. IX, pp 58G-598. As acplied to fivers or fabrics or membranes, this process includes two steps. The first oten is the activation of the substrate by precipitating a catalytic nob e metal nu. ‘«atiun sites on the substrate surface. This is done by first soaking the substrata ir 4 solution of a low-oxidation-state reductant cation, and then soaking the substrz‘e in a soiution of noble metals cations, preferably a solution of Pd++ cations, most creferable an acidic PdCl, solution. The low-oxidation-state cation reduces ths nope metal cations to the noble metals themselves, while being oxidized to a higher oxidation state. Preferable, the reductant cation is one that is soluble iit both the initial low oxidation state and the final high oxidation state, for example =i ++, which is oxidized to Sn++++, or Ti+++.

Which is oxidized to Ti++++.

The second step is the reauction. in cose proximity to the activated substrate, of a metal cation whose revocticr is catalyzed by a noble metal. The reducing agents usea tJ reduce the ii = vical, are molecular species, for example, formaidehyde in ihe case of Cur+. Because the reducing agents are oxidized, the metal cations are terme ‘oxidant cations’ herein. The metallized substrate thus produced is characlersed m1 that their metal plating is bonded directly to tne substrate.

Based on the process descrbeo anove. it is aso possible for someone familiar with the art to identify the oxidant slaies oy thai colors. When the substrate is allowed to float in a copuwer solution =r reduction as described above, different colors are obtained on each side of th2 substraie. The topside of the substrate is the shiny bright copper (red/yeliow) cc or cinaracter.stic of elemental copper - Cu.

The bottom side cf the fabr:c is a blac~ color wach i5 characteristic of CuO. Any substrate located under the top subst ete aiso shows a black shade on its upper side.

In the process descr ned herzir ~h=nges are nade to the process to allow the plating of a cellulose fiber or surirate wilh 2 different cationic species of copper than elemental copper or coppe: orice (Cu ~ black).

This form of electro-irss plating ~0cess imvoves the reduction of a cationic form of copper froin a copper solution sit as copper sulfate or copper nitrate on to

“g : a prepared surface on fibers or a sutsrate. The fibers or substrate to be plated must first be soaked in a solution contzning at least one reductant cationic species having at least two pcsitive oxidaticr: *ates, then at least one cationic species being in a lower of the at least two positive oxidation states. The fibers or substrate are then soaked in a soluticn containing at least one noble metal cationic species, thereby producing an activated surface.

The fibers are then exposed tz at jeast one oxidant cationic species in a medium in contact with the activated s:..face. A 1educing agent is then added and the copper reduces itself from the soii::icn on to the surface of the fibers. Without the following changes, the fibers «: substrate produced using this formula demonstrates an elementai copper cu:iiy on the fibers which are on the top of the fiber or substrate pack and black color:a fibers below and throughout the fiber or substrate pack.

As stated hereinbefore, in ora: ~ « obtain a material that is effective for preventing, minimizing and raimoving w wles and groviaing for smeo:her and more robust skin surfaces a cationic speci:.. Ff cupper hiust be obtained. The effective compounds of copper must contain &:i 121 a Cu ¢l) or Cu (ll) species or both. To insure obtaining these species on celuiue2, the d++ must be applied so that there is equal saturation of all fibers at the sare tine, e.g. by soaking and squeezing. If a large fiber pack is dropped into the Pd += solution, the first fibers to hit the solution will absorb more of the Pd++ solution 1 an aiher paris of the pack, which will upset the cationic copper deposition. in additon, ihe fibers must be washed between the first process involving the Sn++ and to second crocess, Pd++, in water. Residual

Sn++ solution left between ihe fibers w+ cause a reduction of the Pa++ directly into the solution between the fitiers and wi: »acw only a rendem reduction of the Pd++ on the fibers which will again effect toe deposition of the copper. While these two points may seem small, they have a die eiizct on tre plating.

In addition, a change is neces; + i the zr dncation system of the copper solution to the process. A side effect of 2 reduction process on to the fibers is the creation of hydrogen. This hydrogen i023 a4 buobies on the surface of the fibers. The hydrogen forme as a rest 7 the :nteracoon in the copper solution with the Pd++ on the fiber surface. If the = :r3gen is not “emoved, by methods known ny per se, such as squeezing, from the surface of the fibers immediately upon their formation, the fibers expose: to the air «ll ive coated with an elemental copper.

The fibers just below the =z.rface of tv =2iomeria! =pper will be black copper oxide. If, however, the hydrcgen is rem: 2d ‘rimediately with their formation of the ‘bubbles, the desired cationic species i= zhtaned throughout the fiber pack. The desired color will be a dark brown whicl; is distinct from the copper metal color or the black copper oxide. A furiher indica’ nn of ihe cationic species is that the fibers will not conduct electricity.

This process yields both a Cu (I) and a Cu (ii) species as part of copper oxide compounds. Analysis of residual crpper oxide powder formed by this process has shown that formed on the surface ar: cupper oxide compounds which are 70% Cu (I), and 30% Cu {li}. These cc. wuuids have been proven tc be a highly effective in the treatment of sores abra::1is and bums. The activity of the copper takes advantage of the redox reaction .» re cationic species with water and allows a switch between Cu (I) and Cu (I) whe ines2 is contact with water. Cu(l) is more effective than Cull) against i4iV while Ci. ‘iy 1s raore stable than Cu(l).

In US Patent Application 10/3358 :¢ carrespording to PCT/IL03/00230, the relevant teachings of which are also i-surporated herein by reference there is described and claimed a device for the achivation of a virus comprising a filtering material, said device having onic coppe: selected trom the group consisting of Cu’ and Cu’ ions and combinations thereof ~<orporated trierein.

In saiu specification there is desc ited ihe olatir.g of cellulose fibers using a copper solution which results in the formi=t.an of copper oxide on the surface of said fibers wherein the process used yieias ch a Cu(ly and a Su(ll) species as part of a copper oxide malecule. Said fibers wer: tier incorporated into a filter which was found to be effective in the inactivation © -}v-1

While the mechanisin of the hydraulic polymeric materials according to the present invention is not fuly understoad. in light of the results obtained, it is believed that when the polymeric rabid 1s brought into contact with a fluid aqueous medium, said medium leaches “2 rationic species of copper from within said polymer and as descibed in PCT4'.U3/00230 the wrinkle effecting activity takes advantage of the redox reaction ©’ i» ~ationic species with water and allows a switch between Cu (il) ard Cu (1) when there is contact with water. Cu(l) is more effective than Cu(il) while Cu(ll) is more st2bie than Cu(l). The Cu(ll) compound will oxidize much more slowly tran the Cu ~ampaund and will increase the shelf life of the product.

As stated hereinbefore, the discovery cof the present invention that materials incorporating water-insolubie copper ccimuouads which release Cu’ ions, Cu®* ions or combinations thereof ucon contact with a fiuid are surprisingly effective in preventing, minimizing and removing wiinkies and providing for smoother and more robust skin surfaces enabizs the proJduciion of an entire new line of products according to the present invention.

Keeping in mind that the produc: will encourage better skin appearance no matter where the fabric touches the cuuvy, the following is a description of some products and the protocols {or their eri: i: 1. A sock knit from either treated pwr or celiviose yarns that can be worn day or night as any cther sock, # ." ii yieid 7esher looking feet. 2. A knit glove that cari be worn v.:i= sleeping that will reduce wrinkles and improve skin softness of the hanas. 3. A face mask or eye-covering mask triat can be worn while sleeping that will improve the facial skin. 4. A pajama made from fabrics eitr 1 «nt or woven that can be worn at night and that will improve general body skir:. 5. A woven or knit scarf made trom =itner cellulose or polymer fibers that can be worn day or night that will imp «ve rieck skin appearance. 6. An adhesive tandage that can be placed on specific pock marks to improve the texture of the skin at the mark. 7. A knit or woven undergarment whether panty, underwear or bra that can be worn day or nignt and will improe we skin texture of the specific area of the body with which it cor.es in corie 8. Bed linens and sleepwea Thes:- va be in the form of a textile made from either a cotton/polyester or cot + “zsed ‘abric where a percentage (can vary from 3% (0 10% ) of the yarn is treated ceiluiose or where the fibers of the yarn are a polymer in either filament cr staple form. The article can be knit such as a cast lining or scuic © can be woven such as a head cover or other article of clothing. 9. Sheath for neck: Thase will pri’ ‘ak v be made from the new breathable polymers that allow for the wicicing, ard dispersion of moisture through them which polymers have been produced with the water insoluble cationic copper oxide particles introduced into the extrusion process.

While the invention will now be described in connection with certain preferred embodiments in the following examples and with reference to the attached figures so that aspects tharzcf may be more fully understood and appreciated, it is not intended to limit trie i vertion to these particular embodiments.

On the contrary, it is iniended to cove all alternatives, modifications and ~ equivalents as may be included within ihe scope of the invention as defined by the appended claims. Thus, the follov.ing examples which include preferred embodiments, will serve to illustrate the praciics of this invention, it being understood tat the particulars shown: ri. by way Gi example and for purposes of illustrative discussion of preferred eri:...mernis of the present invention only, and are presented in the cause of providing; what 1s believed to be the most useful and readily unaerstood description of for .aion procedures, as well as of the principles and conceptual aspects of the. iv aiion.

In the drawings:

Figure 1a and Figure 1b are photogranhs of the heel of a foot of a patient taken before and after application thereto of = sock accoraing to the present invention as described in example 3 here nafter;

Figure 2a and Figure 2b are photogra.ti-s of the two hands of a volunteer taken before and after wearing a pair of gic.es according to the present invention as described in example 3 hereinafter;

Figure 3 is an eiectron microscope photograph of a polypropylene breathable film which was prepared by introcucing 1% "iar insolub = copper oxide into the master batch before extrusion of the film, to for « i'm having microscopic water insoluble particles of ionic copper oxices in pow: od farm, embedded directly therein with a portion of said particles being expose =: bretiuding fom surfaces thereof: and showing up as white dots in the electron ~'croscope pinotograph thereof:

Figure 4 is an electron microscope chotagranh of a polyester fiber prepared by introducing 1% water insoluble copper ide into the master batch before extrusion of the fiber, to form fibers having arcruscapic watsr insoluble particles of ionic copper oxides in powdered form, embeckied directly therein with a portion of said particles being exposed and protruding ‘rom surfaces thereof, and showing up as white dots in the electron microscope pi“tograph thereof;

Figure 5 is a graphical representation of 2a S day follow-up regarding Erythema;

Figure 6 is a graphical representation of a 35 ay vollow-up regarding Erythema;.

Figure 7 is a graphical representation of 9 day treatment regarding scaling;

Figure 8 is a graphical representation of & 36 day follow-up regarding scaling;

Figure 9 is a graphical representation ¢ = 9 day follow-up regarding fissuring;

Figure 10 is a graphical reprasentaticit of & 39 day follow-up regarding fissuring, and;

Figure 11 is a table setting foith the oouervec resulls 00 wrinkles of women using a pillowcase prepared according to the 1 2uerit invennion "EXAMPLE 1:Preparation oi fabrics fru; trated cellulose fibers: 1st. A cellulose fiber is cinosan for na desired end use. Such fibers as,

Tencel, or acetate, or viscose or raw Cris: dre among the fibers that can be used. It is necessary to nuie that the + ers must be celiulose based as the plating will use the OH groups on the surface for initial attachment to the fiber. The length of the fiter chosen ix a function of the end use and is common knowledge in the industry {1 = long staple fibers are mixed with other fibers that have the same length such as in the case of combed cotton, etc.). 2nd. The fibers pass through the var. .s cnemical processes as described herein: 1. Fibers are prepared in a thin m= :: assure a deposition of the correct cationic species. 2. The mat is soaked in a soruti-. i =f T.n Sichloride ana hydrochloric acid. The mat is allowed to soak fri = smali anount of time to insure complete absorption.

3. The mat is then squeezed to re-nove almost all liquid and washed in water to assure the removai of all the tii solution. 4, The mat is then placed in a ver “lute solution of palladium dichloride and hydrochloric acid. While other me:« sais can be used for this process, palladium was found to be the most efficent. 5. After removal from the palladi.m dichloride the mat is once again washed and again squeezed to assur: ‘hi removal of all extraneous liquid.

At this point the mat will have changed color to a lignt tan. 6. A chelated copper suifate soiuinn is prepared using copper sulfate, polyethylglycol, and EDTA. The pH ci ihe solution is controlled by adding sodium hydroxide to the scution. A redciant is added to the copper sulfate solution. While many reductants can 1.¢ used formaldehyde was chosen as the preferred compound. 7. The mat is placed :1 the suiLuen @nd allowed to go through the process which can take wi to 7 re-.6s io ocr. The mat must be squeezed or patted down curing the plating process. 8. The mat is then washed in wat: 2 remove excess dust and allowed to dry. 9. At the end of the process, the fibers ace plated with an ionic form of copper and have a dark brown mixed shade co's’. 10. The fibers are blended with othxr fibers (the sane untreated or other fibers) so that the end product conizins unly the amount of the desired copper oxide plated fibers. In some cases a 1% blend/99% other fibers is necessary and in other csses as mut as 30% treated fibers/70% other fibers or any combination is prepared This can be done in several ways all known to people familiar witir the art of “ext |e vari spinning. 11. The mixed fibers yun through 4: :.ormal textile processes, ie. in the ‘case of an open-end spun product; caring, s.ver $0IFINING. 12. Once yarn is obtaine.J it can be «#21 woven or knit depending on the desired end-use.

13. Fabrics can be used as are or trey can then be dyed or printed but not bleached, as this will cause the rapper “o disconnect itself from the cellulose substrate. 14. The textile fabric car: than te -2asily ccnverted into the desired product.

EXAMPLE 2: Preparation of fabrics or films from treated polymeric materials:

Example 2a: Preparation of fabrics:

A 1. A polymeric material is chosen ic the desired end use. Such fibers as polyester, polypropylene, polvethylene, rivian 63, nylon 5, etc. are among the fibers that can be used. The fiber can be form: ¢ into either a filament form or short staple form.

A 2. A master batch is prepared using the same base material as the desired yarn into which a copper oxide powder is addad. For most textile end uses the master batch may have a 20% - 25% concentra on of the copper oxide powder included in it. This master batch will be added te * »: d¢'ymer wzing extruded and diluted so that only about 1% or 2% «i the maie 1a” wir be in the finished yarn. A certain amount of this copper will appear on i ¢ suriace of a polymeric fiber and can be observed in an electron microscope picture.

A 3. Ifthe fiber is a filament fiber it can be woven or knit to produce a textile.

A 4. If the fiber is a staple fiber it can ue mixed with other fibers just the way the coated fibers described above are mned and then follow the same process of manufacturing.

A 5. Once yarn has been completed, ii zar woven cr knit into a textile product which follows the normal and accepted systems for finished product conversion.

Example 2b: Preparation of films or siieaths.

B 1. A polymeric material is chosen for the: desired end use. Such polymers as polyester, polypropylene, polyethylene, nylon 56, ny'on 6, etc. are among the polymers that can be used. The polymer: materig! can be formed into either a film, or a sheath.

B2. A master batch is prepared usi¢ the same pase material as the desired polymer into which a copper oxide pov.ue: 1s added. -or must end uses the master batch may have a 1-3% concentration ot ire copper oxide powder included in it.

This master batch will be added to the pciymer being extruded. A certain amount of this copper will appear on the surface if a polymeric film or sheath and can be observed in an electron microscope pict: ©2

Example 2 C: Preparation of fibers:

A total of 500 grams of a polyamide bi-component compound were prepared by heating the two beaded chemicals in separate baths each at 160 °C.

The two separate components wer2 then mixed together and allowed to stir for 15 minutes until the mixture appeared tc be homogenous in color.

The mixed chemistry was again -ivided into two separate pots. In one pot, grams of a mixture of CuGU and Cux{ pcwder was added yielding a 1% mixture.

In the second pot 6.25 grams of a mixtu: e of CuO and Cu,0 were added yielding a 0.25% mixture. In both cases, the temperature of 160 °C was maintained. The compounds were stirred until they appeared homogenous in color.

The two mixtures were run througr a spinneret with holes that yielded fibers of between 50 and 70 microns in diame.<i. Since tne Cu++ releasing copper oxide powders were ground to particles of ‘ess ian 20 rierens no obstructions in the spinneret holes were observed. The exu'.ced {bers were air-cooled and spun on to cones.

The resulting nylon fibers having Cu++ releasing copper oxide incorporated therein can be used in many of the appiit:aiior of the present invention including in gloves or socks, and scarves.

As will now be understood by rersons skiiied in the art, the difference between the normal process of manufacunng any synthetic fiber and this process, is the addition of the Cu++ releasing upper oxide powders in the raw materials, and for many uses of the prasent inve: ®izn such polymers as polyester, nylon and polypropylene can be interct-angeabply : se.

EXAMPLE 3: Regeneration of Heei Area of Zoot:

Referring to figures !a and 1b, there are seen before and after photographs of the heel and sole area oF a fcot cf : woieneer, wherein in figure 1a it can be seen that said area is wrirklea and r achy A polyester sock according to the present invention having 1% of fibers «~ nsoluble copper oxide compounds of Cu* and Cu’ incorporated into the bottom =: andi nee&i area thereof was worn for 6 days. At the end of said period a furth ohotograph was taken as seen in figure 1b, and as can be seen the skin is mn robust softer less patchy and has fewer wrinkles even though this is not read! sean in the attached black and white photograph.

EXAMPLE 4: Reduction in Wrinkles in ack of Hand Surfaces:

Referring to figure Za, there is seen a photograph of both hands of a volunteer. Said volunteer then wore : cciton giove according to the present invention on his left hand oniy, for a pericd of 3 nights and for about 10 hours each night. Said glove was made of 97% cotton and included 3% of cellulose fibers according to the present invention, wherain said fibers were coated with insoluble copper oxide compounds of Cu* and Cu". As can be seen in figure 2b, after only 3 days the left hand of the user wes mug: .incother and the wrinkies were much less pronounced.

EXAMPLE 5: Ciinicai Testing.

Dr. Michael S. Smith, & Board C+ feu Neurulegist with a Master's Degree in

Experimental Statistics, was asked to anayze the effectiveness of socks prepared with a lower panel of fabric incorporatrict waie:-insolubie copper compounds which release Cu’ and Cu’ ions, upon a va aly of podiatiic conditions, 1.e. erythema, scaling, fissuring, odor and ederna. Onivzr indications such as itching and burning, vesicular eruptions and drainage were sted and recorded although these are not cosmetic issues.

One group of paiients was sti, ana the results were compared to the experierice the podiatrist iad with ga cits with simiar conditions who were not treated with socks according to tne pres. nt vention.

RESULTS:

The following results are aii con.derad statisticaliy significant, meaning that there is credible medical evidence ha veatment with the socks according to the present invention is effective inthe pert fllow us studied, since the confidence interval of all the results did not ince: =» 7) 3nd the p-values for ail results were <0.001.

ie)

Demographics:

There were 56 patients in all, 1 women and 39 men. The average age of the group was 58 with a standard « ¢ ation of 16 years (range 21-85 years).

Twenty-one (21) were diabetic, 21 were older than 65, and 24 were followed more than one time.

Variables:

Seven measures were studiec: erythema, burning and itching, edema, scaling, vesicular eruptions, fissuring, zrainage and odor Only scaling was present in all 56 patients, with erythema in 51 (see table) Edema (6), Odor (5), and drainage (3) were the least common ables. “Long range follow-up referred to having been evaluated more than one time after use of the socks. There was a three level ordinal scale used: preserd, improvement, and resolved. Movement along this scale (from “present” to “irwroved” or from either of the first two to ‘resolved”) was considered a posite sien niovement the other way (from ‘improved’ to “present” considered ¢ rogaine sip if 3 patient was considered resolved on the first visit after wearir¢ 11s socks, mat individual could at best be scored a “same” for lorig-term folic pu. Therefore, “same” could be equally considered to be "holding smprovemer {". The average length of time in the long term section was defined as being the iirre vetween the first visit and the date when the last comment was made about the stient. Only patients who had a specific problem at the outset of the study wer: ouriied rater. In no instance did a patient who haa no specific problem develop ne. Ir the .nstances of edema, odor, and drainage, the sample sizes were too +1 a. {o araw any conclusions, although the results were tabulated.

Example 5A: Erythema (51 patients):

A1. All 51 patients improved: 22 (42%) resoived completely over an average period of 9 days (range 4-28 days). The 95% “tiidence interval for resolution was (0.28, 0.58). This result means that while v2 dart know the per cent of complete resolution for the entire popuiation (the ararreter). we are highly confident it lies in the interval between 29% and 58%. !f . «- krw in advance that no patient would normally improve without cther treat nis in this time frame, than the results obtained are highly significant; that is, ru: due to charice.

as

The results of this test are shown in Figure &

A2. Longer term study (22 patients):

Nineteen (86%) maintained their imps varie t or resolved, 95% CI (0.65, 0.97).

Three patients (14%) did net maintain iv or Zvernent or reverted to “present”, 95% Cl (0.03, 0.34). The average length of fo'.w-up was 36 days. Diabetics and patients older than 65 shared in the improvement, both early and long-term.

The results are shown in Figure 6.

Example 5B; Scaling (56 patients):

B1. Fifty-five (55) of the 56 improved (%8%). 5 resolved (9%), and 1 stayed the same. The 95% confidence interval iar some improvement is (0.90, 1.00); for ~ resolution (0.03, 0.20). Both of the p-values are highly significant for efficacy.

The results are shown in Figure 7.

B2. Longer term study (24 patients):

Twenty-one (88%) held imgrovement or resolved, 3 reverted with an average follow-up of 24 days. The u5% confitiznae irterval is (J 68, 0.97) with a p-value <0.001. Again, diabetics ai:d elderly sharzd iii the improvement.

The results are shown in Figure 8.

Note: the follow-up graph has the same scale as the foimer graph to facilitate comparison.

Example 5C: Fissuring {37 patients):

C1. All 37 patients improved; 15 (40% resvived completely with an average follow- up of 10 days, 95% Cl (0.25, 0.58). Tins is highiy significant.

The results are seen in Figure 9.

C2. Longer term study (17 patients).

All 17 patients improved, € (35%) rescived completely in an average foilow-up of 39 days, 95% CI (0.14, 0.62). Again, diabeucs and elderly shared in the improvement.

The results are seen in Figure iC.

Example 5D: Edema (6), Drainage i} anc Odor (5):

Three patients with edema miz-oved 1 rescived. All three patients with drainage improved: 2 resuived. Three i tha five pat.ents with odor improved; two of them resolved.

DISCUSSION:

The purpose of the study was to see if patients with a variety of podiatric ailments would improve only by wearirz socks having a fabric panel according to the present invention. One issue in the treatment of the above conditions is compliance in obtaining and using the treatment (special socks). A related issue is : the proper application of treatment (special socks) on the plantar aspect of the feet and in the interdigital areas. 1. For purposes of these examples the following was assumed in the analysis of the data provided: a. The patients were a reasonable. representative sample of the population of patients with these conditions. There was no information received that wouid contradict this assumpiici. Tnere were aien, women, elderly, young, diabetic, and non-diabetic patients. b. The patients were independer:t of cine another: that is, the selection of one individual had no eftect upor: it: seiation of another. c. The definitions of improvemen: and resolution were constant for each patient. d. The samp'e size was known ar: aporupriate to perform analysis. e. Outcomes could be defined as hohotornous.

The presence of these assumptions =llowed a binomial probability distribution to be used. 2. There was no control Group reported, nowever, information was received stating that the podiatrist believed it unliki:ty that any patient would have resolved or improved in the time frame of ta= s.udv only by wearing his or her regular socks. Given such information, ail wi the: above results, would be considered statistically significant, meaning th«t there is medical evidence that treatment with fabric panels according to the praesent invention is effective in this period of follow-up.

It is important to understar.a the vocabu: ary used in describing the study: « Population: the group about which: one wishes io learn In this instance, the population are ail patients with the ab. ve iis 2d foot conditions.

« Sample: a subset of a population. « Random sample: A subset chosen w*eare each member of the population has a defined, non-zero probability of being c-csern » Parameter. a numerical measure of the population. « Statistic: a numerical measure of the samgle. « p-value: the probability that we would obtain the specific sample statistic (or one more extreme) if the nul! hypothesis (hypothesis of no change) were true. In the context of this study, a p-value of less than 0.001 means that the probability of obtaining these results by chance alone 1s less than 1 in 1000. Typically, 1 in 20 is considered the “cut-off” point. Minitab =oitware does not compute p-values to four decimal places, so many of the values cbtained here are even smaller. « A confidence interval contains a range of plausibie values for the parameter. We call it a confidence interval, because while Lnkncwn, the parameter does exist, and the interval either cor.ains or ¢u+: ne comvain the parameter. It is NOT a probability question. For this study, it + + assume tha: 1c patient would improve in the time frame studied with convenuo:iei treatment then so long as ihe interval does not contain 0, the results are s-gnificant, since no plausible value of the parameter is 0. If some other propo tion were postulated for improvement, then any intervai that did not contain ths! padicular value would be considered significant. In this study, with the abi: = infesmation, all areas reached statistical significance. « Circle of inference: We sample from a vopuiation, obtain a result (a statistic), and use that value to infer someching abou: 3 parameter which is part of a population.

Population. =» Sample 1 NG rarameter. €Giahstic

It is important to recognize tha! woo can seiaan identify all members of a population, so that its numerical measur, a parameter, remains unknown.

For this study, since we cannct vrow all memoers of the population, the result of the sampie, the prooortion im: ved (or resolved), is used to say a similar proportion of the population would ne wnproved as well. If the sample is appropriately chosen, then the estimate has value. We must realize, of course, that other samples would lead to other results, so that there is a range of plausible values that samples coulc conceivably rave, and our sample result was one of those potential values, as described eb 2

CONCLUSION:

Compared to historical controis patients with socks prepared with a lower panel of fabric incorporating water-ins.i ble copper cempounds which release Cu’ and Cu” ions as according to the pres~:.7 invention, had significant improvement or resolution in the following conditions:

Erythema

Fissures

Scaling

Edema

Odor

Moreover, since rieay 40% +. 7 & | of {ne group was either diabetic or older than 65 (10 were boy digbeds 1d oar han 68) this study is statistically significant for improvement ar resaived ir 2ll tha above conditions for people with diabetes, including elderly aiabetics.

As is known, erythema is charai-enzed by a redness of the skin caused by dilatation and congestion of the capiliz<ies and is often a sign of inflammation or infection, and ther=fore is a cosmetic :- carn:

Scaiing is a healing issue whet» &iles to psonasis of a microvial nature which is ameliorated by the use of ite vreuucts of ihe present invention and is certainly a cosmetic issue.

Edema is an observable swelling 1 certain parts in the body and most commonly occurs in the feet and leg: wivere it also is referred to as peripheral edema. The swelling is the result of th rouulation of excess fluid under the skin in the spaces within the tissues thet =r: citside of the blood vessels and the reduction thereof is faciiitalicd by the =~ “0.3 nd proaucts of the present invention.

Fissuring is a brea< nn the ski~ ssialy where it joins a mucous membrane producing a crack-like sore or uicar &: © MUS is iso a cosmetic issue which can be dealt with according to the r.resent inve on

Odor is a major cosmetic issue “»1ich can be dealt with, with the products and methods of the present invention.

EXAMPLE 6: A Study of tlic effect ot . i5:l.0v.-case on face wrinkles:

Seventeen (17) women whe reguarly use skin treatment products were given a pillowcase which was forme: fiom a fabric having fibres incorporating water-insoluble copper compounds “waich release Cu” ions, Cu’ ions or combinations thereof upon contact with a fiuid and were asked to be photographed before the test, at the end of the 1st week, at the end of the 2nd week, and again at the end of 4th week after sleeping each night with a pillow case prepared according to the present invention. Al the end of Lie 8% week tha candidates were asked to telephone and notify the receiver of the nfarmation if there was an improvement or deterioration in overail skin appearance. i he candidates were asked not to use any nightly oils or creams but just to wash ot the face before going to sleep at night.

The purpose of the evaluation was to otserve the effect of the pillowcase on crow’s feet, fine wrirkies and fine ass on tres toe only. The method of cbservation was photographic using a 3.4ps! Jyigital can. 1 iri reatural bght.

Candidates were instructed 10 keep the pinowcase mn coniact with either side of the face when sleeping. The piiiowcases weie washed once a week in ail cases. The candidates were instructed to wash their face with the same soaps that they normally use but not to use any oils or ft:=heners before going to sleep.

All candidates were aged betw=¢: 45 and 50. None of the candidates were on medication. At least 2 of the candidates are known to be smokers.

Far the purpose of the test, a ue-matologist was asked to observe if there were any possiblz negative effects. Mo nevative effects were observed which confirms the biccompatibility tests done previousty. A panel of 10 different women were asked to evaluate {re nhotographs + nth ‘he following values: 1. No improvement symoolized by on the &itached sheet 2. Slight improvement sy nibolized by “3” en the attached sheet 3. Improvement symbolized by “C" un the attached sheet 4. Marked improvement sympclize: + U7 ori fhe atlached sheet cied

The names of the 17 candidates zre available in a separate file and on the chart attached hereto as Ficure 11 are 7 3vresented as numbers 1-17. The names of the 10 judges are available un a separ > ile

As can be seen from the results recorded by these independent judges, as shown in Figure 11, over time analysis of the face showed overall significant improvement for the reducticn of crow’s f22t wrinkles, fine lines, and in some cases mottled hyper-pigmentation (liver specs). In ali cases there was an overall improvement in skin appearance and texcure.

It will be evident to those skilled ir the art that the invention is not limited to the details of the foregoing .iustrative exarnples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired tnat ie present embodiments and examples be considered in ail respects as illustrative asd fot restricave, reference being made to the appended claims, rather than to «ao fecregong description, and all changes which come within (ie msaring and ang: of equivalency of the claims are therefore intended to be embraced theie.::

Claims (35)

WHAT IS CLAIMED IS:

1. A cosmetic method for, prevening. minimizing and removing wrinkles and providing for smoother and more robust skin surfaces comprising applying a material incorporating water-insciuble copper compounds which release Cu’ ions, Cu" ions or combinations thereof upon contact with a fluid to a body surface to be treated.

2 A method according to claim 1 wherein said material is a fabric having fibers incorporating water-insoluble copper compounds which release Cu’ ions, Cu™ ions or combinaticns thereof upon contact with a fluid.

3. A method according lo claim 1 ‘anerein said rnat2rial is a polymeric film having microscopic water soluble particles of ionic copper oxides in powdered form, embeded directty therein with a portion of said particles being exposed and protruding ‘ron surfaces thereof, which particles release Cu’ crs Cu'’ ions or combinations thereof upon contact with a fluid.

4 A method according to claim 1 wiierein said maierial is a polymeric finer having microscopic water soluble particies of ionic copper oxides in powdered orm, embe:ided directly therein with a portion of said particles being exposed i.) protruding fiom surfaces thereof, which particles release Cu’ icnis. Cu ions or combinations thereof upon contact with a fuid.

5. A method according to claim 1 wherein said material is a polymeric filament having microscopic wie nsioluoie particles of ionic copper oxides in powderea form, empedded directly therein with a portion of said particles being exposed ure protruding irom surfaces thereof, which particles release Cu’ uns, Zu" ions or combinations thereof upon coniact with a fiuid.

6. A method according to claim 4 wharain said material is a polymeric sheath having microscopic wats insoluble particles of ionic copper oxides in powdered form, embeded directly therein with a portion of said particles beir:: exposed «wi protruding from surfaces thereof, /

which particles release Cu’ ions Cu” ions or ccmbinations thereof upon contact with a riuid.

7. A cosmetic methoc accord . > ulaim 1 wherein said material is incorporated in a pillowcase.

8. A cosmetic method according to claim 1 wherein said material is incorporated in a bed sheet.

8. A cosmetic method accordiry to claim 1 wherein said material is incorporated in an ai least partic: face mask.

10. A cosmetic method according to claim 1 wherein said material is incorporated in a scarf.

11. A cosmetic method according to claim 1 wherein said material is incorporated in tubular sheath for removable positioning on the neck of a user.

12. A cosmetic methcce accords wy ciagirn 1 wherein said material is incorporated in an -longated © ow avi g interlocking means provided at opposite ends thereof for adjusi soe attachment surrounding a body portion of a user.

13. A cosmetic methoa according ‘0 claim 1 for preventing, minimizing and eliminating wrinkles comprising «oplying to a wody surface to be treated a polymeric material formed fron: - poiymeric component selected from the group consisting of a polyarniue: @ oolyester, an acrylic and a polyalkylene, said material being ni the form o1 a fiver, a yam, a sheath, a filament, or a sheet, and having microscopi water insolubie particles of ionic copper oxides in powdered form, embedded directly therein with a portion of said particles being exposed and protruding from surfaces thereof, which particles release Cu’ ions, Cu'" «wns or combinations thereof upon contact with a fiuid, to a skin surface 0 «= t €ealed.

14. The use of water-insoluble cci't= compounds which release Cu’ ions. Cu" ions or combinations treved! upon contact with a fluid for the manufacture of 1 rnateriai 1& brought in contact with a body surface for preventirq minimiz::y and eliminating wrinkles.

15. The use of water-irsoluble ccaper compounds which release Cu’ ions, Cu” ions or combinations taereof upon contact with a fluid for the manufacture of a fabric 0°» «uitradsd film filament or sheath to be brought in conta:t with a toi. surface for preventing, minimizing and eliminating wrinidles.

16. The use according to claim 15 of fibers incorporating water-insoluble copper compounds which relezse Cu’ ions, Cu™ ions or combinations thereof upon contact with a fii tor the manufacture of a pillow case for preventing, minimizing and reinving wrinkles and providing for smoother and more robust skirt surfaces.

17. The use according !» claim 15 i! a polymeric fim having microscopic water insolubie particles of ionic corwer oxides in powdered form, embedded directly therein with a portion of said particles being exposed and protruding from surfaces thereci, winch particles release Cu” ions, Cu” ons oi combinations tnereof Coun comast with a fluid for the manufacture of a material for preventing nircizirg and removing wrinkles and providing for smooti-er and mu: “abt.st skin surfaces.

18 The use according to claim ** wfierein said fibers are polymeric fibers having said compounds incu porated therein and protruding from the surfaces thereof.

19. The use according to claim 1; wherein said fibers are coated with said copper compounds.

20. The use according to cian. 15 ¢f fiers incorporating water-insoluble copper compounds which rele =i Zu” ions. Cu'" ions or combinations thereof upon contact with a ‘wa ior ne raanufacture sleep attire for preventing, minimizing and removing wrnkies and providing for smoother and moi e robust skin surfaces.

21. The use accordir-: to ciaim ©” wnereir sad fibers are polymeric fibers having said ompounc: incorporated therein and protruding fron the surfaces the-eof

22. The use according to claim 27 wherein said fibers are coated with said copper compounds.

23. The use according te claim 158 = a n3lymeric film having microscopic water insoluble particles of ionic copper oxides in powdered form, embedded directly therein with a portion of said particles being exposed and protruding from surfaces thereof, which particles release Cu’ ions, cu” ions or combinations thereof uron contact with a fluid for the manufacture of a glove for preventing, mirin.zing and removing wrinkles and providing for smoother and more robust skin surfaces.

24 The use according to claim 15 of a polymeric film having microscopic water insoluble particles of ionic copper oxides in powdered form, embedded directly therein with a portior: of said particles being exposed and protruding from suriaces thereof which particles release Cu” ions, cu” ions or combinations thereof u,.wri contact with a fluid for the manufacture of sheath for preventing, minin: xing and removing wrinkles and providing for smoother and rnore robust skin surfaces.

25. The use according to claim 1& of fiers incorporating water-insoluble copper compounds which release Cu’ ions, Cu™ ions or combinations thereof upon contact with a fluid for the manufacture of a fabric to be brougnt in contadi with a body surface for preventing, minimizing and eliminating wri ies.

26. The use according to claim 27 wheiemn said fibers are polymeric fibers having said compounds incorsorated therein and protruding from the surfaces thereof.

27. The use according lo claim 25 wherein said fibers are coated with said copper compounds.

28. The use according © claim 15 7 avers incorporating water-insoluble copper compounas which +=as2 Gu’ ions, Cu’ ions or combinations thercof upon contac: with a flue, tor the manufacture of an at least partial face ir.:xx for vreventing, minimizing and eliminating facial wrinkles as

29. The use according to claim 15 of fibers incorporating water-insoluble copper compounds which release Cu® ons, Cu™ ions or combinations therec® ugor: cot ath i: fluid for the manufacture of an elongated panel having .nterlocking means provided at opposite ends thereof for adjus*able attachment surrounding a body portion of a user.

30. The use according to claim 15 of fibers incorporating water-insoluble copper compounas which ie'ease Cu’ ions, Cu™ ions or combinations therecf upon cont with a tiuid for the manufacture of socks for prevening, minim. ong and removing wrinkles and providing for smootner and more robust skin surfaces.

31. The use according to ciaim & of fibers incorporating water-insoluble copper compounds which release Cu’ ions, Cu™ ions or combinations thereof upon contact with a fiuis! for the manufacture of a terry cloth material for preveriing. nivimizing a: removing wrinkles and providing for smoother and more robust skin -arfaces.

32. A method according to claim i wherein said macerial is a polymeric film having microscopic wate: insoiuble particies of ionic copper oxides in powdered form, embedded directly therein with a portion of said particles being exposed « * protruding from surfaces thereof, which particles release Cu+ nis Cu++ ions or combinations thereof upon contact with a fluid wherwir. said film has the ability to disperse liquid through osmosis.

33. A method according to claim * wherein said material is a polymeric film having microscopic water inscluble particles of ionic copper oxides in powdered form, embedded directly therein with a portion of said particles being exposed 17. protruding trom surfaces thereof, which particles release Cu+ ors. Cutt ions or a combination thereof upon contact witir a fluid «erwin sala “lm has micro pores perforated through ut to allow “= tha escape of excess liquids.

a0

34. A method according to claim ° wherein said material is a hydrophilic polymeric material.

35. A method according to ciaim * whereit: said material is a hydrophobic polymeric material. :