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Publication numberUS2606325 A
Publication typeGrant
Publication dateAug 12, 1952
Filing dateAug 1, 1949
Priority dateAug 1, 1949
Publication numberUS 2606325 A, US 2606325A, US-A-2606325, US2606325 A, US2606325A
InventorsLeonard Fred, Cort Irving, Carl A Nielson
Original AssigneeLeonard Fred, Cort Irving, Carl A Nielson
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Age and stain-resisting article of plasticized polyvinyl chloride
US 2606325 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Patented Aug. 12, 1952 AGE S-TAIN-RESISTING'ARTIGLE F Y r As rIoIzEp POLYVINYL CHLORIDE z ,CarlgA. Nielson, Takoma. Park, and Fred Leonard, V V "Silver S=pring, Md., and Irving Cort, Washington, D. 0.,assignors to the United States of America as represented by the Secretary or the 2 Claims.

The invention described herein may be manufactured and used by or for the Government for governmental purposes, without payment to us of any royalty thereon.

There has been made in recent times marked progress in the production of gloves'or coverings for prosthetic hands, whichgloves simulate in high fidelity the appearance and texture of a natural hand, thereby renderinginconspicuous to an observer the deformity resulting from' an amputation and use of an artificial or prosthetic hand.

Such gloves essentially duplicating the appearance of a natural hand in color and surface marking's are being obtained by molding, or casting a vinyl chloride polymer and plasticizer therefor in a seamless, one-piece metal (nickel) mold. and heating the cast resin while'in the'mold to an elevated temperature .to f effect solution of the swelled or gelled resin in "the plasticizer and developthe maximumtensile. strength and tear resistance. Theglove then is removed from the mold and pigmented interiorly to match the .color of a natural mating hand;

'In the course of use, the glove comes into contact with many different. varieties of materials which tend to stain or to. discolor "the glove'in a permanent manner, such straining detracting from the appearance and wearing qualities of the No Drawing. Application August 1,1949, Serial No. 108,046 j 1 (om-'1)- v ".jf rantefliunaer the act of March :3, 1883, as Y 'amerl ded April 30, 1928; 370 O. G. 757) glove. It has been foundin practice that a plasticized polyvinyl chloride glove is stained irreversibly by. a wide variety of materials. This staining is due to the high solvent power of the plasticizer in the composition towards various oil-soluble dyes used in shoe polish, ball-point ink, and many other materials. T

Not only in connection with the production of gloves but in connection with many other applications of vinyl resins, continued advances have been made in the technology oi. vinyl resins through modifications, combinations and development of improved plasticizers, pigments and processing. Through these advances, many uses for such resins have been found and exploited, such as shower curtains, raincoats, umbrellas, furniture upholstery, and flooring material. Military, uses for the resins include gun covers; tent windows, coated fabrics, maps, and vinyl coatings on metals. The use. of the. vinyl resins in the aforesaid cosmetic gloves for amputees, both civilian and military, is a very recent use of such resins.

While many advantages may be listed in favor of plasticized polyvinyl chloride-type resins, there are several disadvantages which arise principally from the inability of the stocks to resist soilage. Incorporation of the above-indicated enhanced 2 properties in polyvinyl chloride stocks would undoubtedly result in increased application and utility. U V

In connection with the use of plasticized vinyl chloride polymers in cosmetic gloves the problem of irreversible soilage is of extreme importance. For example, gloves" in by amputees over an extended period of time tend to become somewhat dark and glossy before: thewearing life of the gloves has become exhausted; and rubbing against newsprint, clothing, or the like which is inevitable during wearing of the gloves, is found to have a' tendency to produce stains which cannot be removed readily by soap andwater or the usual solvents without producing undesirable effects.

The present invention provides a process for preventing the deleterious effects of irreversible soilage and. aging on plasticized polyvinyl chloride stocks;and whilemot-limited to cosmetic gloves, the invention is of especialapplicability thereto, as it affords full projtee on without obliterating or obscuring any offthe finesurface details or natural appearance which characterize such glgves produced'from. plasticized polyvinyl chlori e. 1 l I In accordance with; theprcsentinvention, it has been found that coatingthe plastieized polyvinyl chloride stocks with ,the" unplasticized; copolymer of ethyl acrylate iand acrylonitrile parts to 10 parts respectively)" 0t high molecular weight, an excellent adhesion of thecopolymer as acoating film to the plasticized polyvinyl chloride.

stocks can be obtained, and the resulting coated stocks remain free fromthe objectionable disadvantages that are found to be. inherent in the polymerized polyvinyl chloride. ,For depositing a flexible film of the 90-10 copolymer of ethyl acryl: ate and acrylonitrile, the flexible; film being free from plasticizing constituents for: the said poly-' mer, it is merely necessary to spraygallatex dispersion or solution-of the copolymer on the plasticized'polyvinyl chloride'sheet or shape and allow it to dry. -An' oven may bev used-to hasten the drying time; Y j

The unplasticized copolymer of ethyl acrylate and acrylonitrile may be preparedby polymerizing these materials together at from aboutl5 C. to about 20C, in asealed container using potassium persulphate as catalyst, and in the presence of a reducing agent, for example sodium hyposulphite, about 0.5 per cent by weight of resins being the catalyst and sodium hyposulphite. An aqueous dispersion of the resulting copolymer is obtained as an aqueous latex emulsion.

More specifically, the emulsion may be prepared Ingredients: Parts by weight Ethyl acrylate 90 Acrylonitrile 1t); Potassium persulphate (catalyst) 0.5

Sodium hyposulphite (reducing'agenwhp f 0.5 Santomerse D (100'partsof} l%) l 1 Water 9 9 The Santomerse D" employed in the foregoing illustrative composition is one of .the series of santomerses manufactured by the Monsanto Chemical Company. The santomerses are salts of:

a homologous series of substituted. aromatic S111: I

" if withlaticesof polyethyl acrylate and other esters of acrylic acid, such as methyl acrylate, butyl phonic acids, used as wetting, spreadingapenetrating, and emulsifying agents."

Production of the emulsion To a solution of the Santomerse D in water contained in a bottle there were added the ethyl acrylate and acryl0nitrile.- The mixture was placed on a shaking machine and agitated until the emulsion appeared homogeneous, this requiring about five minutes. The persulphate and mmsulphate were added,the"bottle sealed and placed in a polymerization bath and rotatedend over end at C. Approximately eight hours is suflicient to obtain complete polymerization. The emulsion of the polymerized monomers thus formed is applied to the plasticized polyvinyl chloride base. The emulsion may be applied by spraying, brushing, or the plasticized polyvinyl chloride base may also be dip-coated. I

It is found, surprisingly enough, that the emulsion when dried to form the-coating, in no way impairs the desired qualitiesof the'plas'ticized polyvinyl chloride sheet or base, and actually renders the base highly resistant'to irreversible soilage and aging. "For example, an uncoated sheet and a coated sheet weremarked both with a ball point pen and rubbed'with newsprint. The

specimens then were washed with soap and water or water-alcohol mixtures, and the resulting stains were easily removed from the coated sheet, whereas the unco'atedsheet resisted removal. A similar result was obtained with a coated plasticized polyvinyl chloride cosmetic glove, as an uncoated glove.

As applied, the coating is a'transparent, elastic film. tightly adherent to the base. Application of the technique of this invention to a molded cosmetic glove made of plasticized polyvinyl chloride shows that the deposition of the flexible ethyl acrylate-acrylonitrile copolymer film causes no impairment of the convincing detail-inherent in the original unsprayed glove.- i I I i The coating is, as has been pointed out above. an emulsion dispersed or solution dispersed copolymer of ethyl acrylate and acrylonitrile. As prepared, the material has a tensile strength of approximately 800900 pounds per square inch, an elongation of approximately GOO-700% and a 100% modulus of 70 pounds per square inch, and good recovery. The low modulus and high elongation compared to the plasticized polyvinyl chlo-' compared with ride glove makes it possible to flex the glove repeatedly without causing thecoating to crack and peel. H T I The adherent bond between the plasticized polyvinyl chloride base and the coating is due probably to hydrogen bonding between the plasticizer in the polyvinyl chloride resin and the rather "active tertiary hydrogen alpha to the negative cyanide 0r carbonyl group in the copolymer. The

adhesive bondis higher in magnitude than the breaking strength of the copolymer.

While the use of the -10 copolymer of ethyl acrylate and acrylonitrile is preferred as the protective coating in accordance with this invention,

the-invention is not limited to the use of such ,copolyn er, as copolymers of varying compositions .may be used, and similar results may be obtained acrylate and other higher alkyl acrylates and copolymers'thereof.

Having thus described our invention, what we claim as new and wish to secure by Letters Patent 1. As anew article of manufacture, a freely flexible base composed 'of plasticized polyvinyl chloride having bonded thereto a continuous and permanent coating film composed essentially of an unplasticized copolymer of ethyl acrylate and acrylonitrile containing approximately 90 parts by weight of ethyl acrylate and 10 parts by weight of acrylonitrile, the film having a flexibility substantially greater than that of the base and characterized by high resistance to irreversible soilage and aging. g

2. As a new article of manufacture, a cosmetic glove for covering an artificial hand and duplicating in high fidelity all surface characteristics of a natural hand the said glove being composed of a freely flexible plasticized vinyl chloride polymer base and a continuous transparent coating film'covering permanently coating the base and composed of the copolymers of ethyl acrylate and acrylonitrile containing approximately 90 parts by weight 'of ethyl acrylate and approximately 10 parts by weight of acrylonitrile, the said coating being continuously'adherent to the base and having a'flexibility substantially greater than that of the base, and characterized by high resistance to irreversible soilage and aging. thereby protecting the plasticized vinyl chloride polymer base against deterioration by aging and irreversible staining.



' REFERENCES CITED vThe following references .are of record in the fileof this patent: f

v UNITED STATES PATENTS Number Name Date 2,060,342 Palicki Nov. 10, 1936 2,332,461 v f Muskat et al. 1...... Oct. 19, 1943 2,453,604 Tenenbaum Nov. 9, 1948 1,473,723 I Nelson June 21, 1949 2,491,097- Feagin Dec. 13, 1949 .4 1.192 Frowde Dec. 13, 1949

Patent Citations
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US2060342 *Apr 4, 1935Nov 10, 1936Palickl Robert CMethod of making coated fabric articles
US2332461 *Nov 2, 1939Oct 19, 1943Pittsburgh Plate Glass CoArtificial glass
US2453604 *Apr 7, 1945Nov 9, 1948Tenenbaum AdeleMethod of making prosthetic articles
US2473723 *Nov 5, 1945Jun 21, 1949Alex A NelsonMethod of making prosthesis
US2491097 *Aug 23, 1946Dec 13, 1949Austenal Lab IncMethod of making synthetic resin articles such as teeth
US2491102 *May 16, 1945Dec 13, 1949Ici LtdCoated sheet materials and plastic compositions therefor
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5258037 *Oct 13, 1992Nov 2, 1993Caspers Carl AProsthetic liner and method of making the liner with a prosthesis socket
US5376132 *Oct 26, 1993Dec 27, 1994Caspers; Carl A.Prosthetic liner and method of making the liner with a prosthesis socket
US5534034 *Nov 1, 1993Jul 9, 1996Caspers; Carl A.Prosthetic polyurethane liner and sleeve for amputees
US5549709 *Jul 26, 1995Aug 27, 1996Caspers; Carl A.Hypobarically-Controlled artificial limb for amputees
US5571208 *Jun 21, 1995Nov 5, 1996Caspers; Carl A.Reinforced prosthetic polyurethane hypobaric sleeve
US5735906 *Jun 11, 1996Apr 7, 1998Caspers; Carl A.Hypobarically-controlled artificial limb with detents for amputees
US5904722 *Jun 2, 1997May 18, 1999Caspers; Carl A.Hypobarically-controlled, double-socket artificial limb with mechanical interlock
US6508842Jan 27, 2000Jan 21, 2003Barbara J. CaspersSocket liner for artificial limb
US6554868Mar 23, 2000Apr 29, 2003Carl A. CaspersVacuum pump and shock absorber for artificial limb
US6645253Feb 21, 2001Nov 11, 2003Carl A. CaspersVacuum pump and shock absorber for artificial limb
US6726726Feb 16, 2001Apr 27, 2004Otto Bock Healthcare LpVacuum apparatus and method for managing residual limb volume in an artificial limb
US6761742Jan 29, 2002Jul 13, 2004Otto Bock Healthcare LpVacuum pump and shock absorber for artificial limb
US6926742Mar 4, 2002Aug 9, 2005Otto Bock Healthcare LpPlate/socket attachment for artificial limb vacuum pump
US6974484Jan 27, 2005Dec 13, 2005Otto Bock Healthcare LpOsmotic membrane and vacuum system for artificial limb
US7670385May 9, 2007Mar 2, 2010Otto Bock Healthcare GmbhInternal socket and fitting system for a prosthesis
US7922775May 23, 2003Apr 12, 2011Otto Bock Healthcare LpPulsating pressure chamber and method for fluid management
US8496715Apr 22, 2008Jul 30, 2013Otto Bock Healthcare LpPneumatic connections for prosthetic socket
US8758449Apr 22, 2011Jun 24, 2014Otto Bock Healthcare LpSocket liner for artificial limb
US9044348Apr 30, 2013Jun 2, 2015Ossur HfProsthetic device, system and method for increasing vacuum attachment
US9072617Apr 30, 2013Jul 7, 2015Ossur HfProsthetic device, system and method for increasing vacuum attachment
US9198780Feb 13, 2013Dec 1, 2015Ossur HfVacuum assisted suspension system
US9364348Feb 28, 2014Jun 14, 2016Ossur HfVacuum suspension system
US9486335Apr 30, 2015Nov 8, 2016Ossur HfProsthetic device, system and method for increasing vacuum attachment
US9615946Jun 18, 2015Apr 11, 2017Ossur HfProsthetic device, system and method for increasing vacuum attachment
US9757256Jun 23, 2015Sep 12, 2017Ossur HfPump mechanism for vacuum suspension system
US20040030411 *May 23, 2003Feb 12, 2004Caspers Carl A.Pulsating pressure chamber and method for fluid management
US20040143345 *Dec 17, 2003Jul 22, 2004Barbara CaspersSocket liner for artificial limb
US20040181290 *Mar 25, 2004Sep 16, 2004Otto Bock Healthcare LpVacuum apparatus and method for managing residual limb volume in an artificial limb
US20070265711 *May 9, 2007Nov 15, 2007Otto Bock Healthcare Products GmbhInternal socket and fitting system for a prosthesis
US20110202143 *Apr 22, 2011Aug 18, 2011Otto Bock Healthcare, LpSocket liner for artificial limb
DE3219648A1 *May 25, 1982Dec 16, 1982Montedison SpaVerfahren zum einarbeiten von 1 zusatz oder mehr zusaetzen in die oberflaeche von gegenstaenden auf der grundlage von vinylchloridpolymeren
U.S. Classification623/57, 526/329.4, 526/344.3, 526/329.3, 2/159, 2/168
International ClassificationC08J7/04, A61F2/54
Cooperative ClassificationA61F2002/5001, C08J7/047, C08J2433/00, A61F2/54, C08J2327/06
European ClassificationC08J7/04L, A61F2/54