CA2341303C - Gelatinous body protection article having a therapeutic effect - Google Patents
Gelatinous body protection article having a therapeutic effect Download PDFInfo
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- CA2341303C CA2341303C CA002341303A CA2341303A CA2341303C CA 2341303 C CA2341303 C CA 2341303C CA 002341303 A CA002341303 A CA 002341303A CA 2341303 A CA2341303 A CA 2341303A CA 2341303 C CA2341303 C CA 2341303C
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- oil
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- therapeutically active
- active agent
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/44—Medicaments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M35/00—Devices for applying media, e.g. remedies, on the human body
- A61M35/10—Wearable devices, e.g. garments, glasses or masks
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
Abstract
The present invention is directed to a vitamin additive such as Vitamin A, B12, C, D, E, incorporated into the thermoplastic material of a sock (12), glove (10) or like body protection article. The thermoplastic material is preferably a block copolymer such as SEBS, SEPS and SEEPS copolymer. Additionally, the thermosplastic material can include natural oils such as grape seed oil, avocado oil, jojoba oil, canola oil, ceramides and aloe.
Description
GELATINOUS BODY PROTECTION
ARTICLE HAVING A THERAPEUTIC EFFECT
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention generally relates to a body protection article, and more particularly, to a body protection article comprising a gelatinous composition having an additive formulation for treating the protected skin. Thi=_ body protection article can include a glove, socks, wrist band, brace for the knee, ankle, elbow and the like, or a shaped pad sized to cover any part of the body requiring delivery of a therapeutic active formulation to the skin. The gelatinous composition helps keep the skin moist while the therapeutically active formulation beneficially affects the well-being of the skin, such as skin sensitive to ultra violet light, burned skin, skin healing after a surgical procedure and the like.
ARTICLE HAVING A THERAPEUTIC EFFECT
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention generally relates to a body protection article, and more particularly, to a body protection article comprising a gelatinous composition having an additive formulation for treating the protected skin. Thi=_ body protection article can include a glove, socks, wrist band, brace for the knee, ankle, elbow and the like, or a shaped pad sized to cover any part of the body requiring delivery of a therapeutic active formulation to the skin. The gelatinous composition helps keep the skin moist while the therapeutically active formulation beneficially affects the well-being of the skin, such as skin sensitive to ultra violet light, burned skin, skin healing after a surgical procedure and the like.
2. Prior Art It is known in the prior art to incorporate an additive into a gelatinous material formed into an article for wearing on the body to affect the well-being of the person. For example, U.S. Patent Nos. 5,098,421;
5,167,649; 5,181,914; and 5,330,452, all to Zook describe various devices comprising a viscoelastic gel pad having pharmacologically active agents incorporated into the gel. U.S. Patent No. 4,842,931 to Zook describes a pad made from a soft viscoelastic gel material containing a high percentage of plasticizing oil for equalizing pressure directed to corns, calluses, bunions and the like. It is also known to apply medication to the skin for the purpose of treating dermal afflictions and for delivering medicine to the body through the dermis. An example of such an externally applied rnedication is disclosed in U.S.
Patent No. 4,879,274 to Kamiya et al. which describes creams, ointments and the like comprising an a-monoglyceryl ether, a physiologically active material and an oily material. The physiologically active material comprises compounds such as drugs, growth hormones and the like including vitamins, for example, Vitamins A and Bõ .
However, what is needed is a body protection article such as a glove, socks, shaped pad and the like that is comprised of a therapeutically active formulation-containing gelatinous composition that imparts beneficial properties to the skin protected by the article. Such benefits include, but are not limited to, reducing scar tissue from burned skin and skin healing from a surgical procedure by maintaining the skin in a moist and lubricated state, treatment of skin blemishes and providing gentle compression to cushion and help absorb shock forces directed to the body.
SUMMARY OF THE INVENTION
The body protection article according to the present invention comprises a thermoplastic, gelatinous elastomeric composition containing a therapeutically active formulation as an additive incorporated therein.
When the gelatinous composition is intimately combined with a substrate such as a cloth material, paper or a polymeric film provided as a piece of clothing or a shaped pad sized to cover a particular part of the body, the therapeutically active formulation is released from the gel to affect the well-being of the person wearing the article. The gelatinous composition is preferable a block copolymer of the general configuration poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-propylene-styrene) and poly(styrene-ethylene-ethylene-propylene-styrene) combined within a plasticizing oil. Preferred therapeutically active SUBSTITUTE SHEET (RULE 26) formulation includes vitamin and/or natural oil additives.
In accordance with one aspect of the present invention, there is provided a body protection article, which comprises:
a substrate; a gelatinous material comprising a block polymer intimately bonded to the substrate; a first therapeutically active agent incorporated into the gelatinous material, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B121 C, D, E, and mixtures thereof; and a second therapeutically active agent incorporated into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof.
In accordance with another aspect of the present invention, there is provided a method for providing a body protection article, comprising the steps of: providing a substrate; incorporating a first therapeutically active agent into a gelatinous material comprising a block polymer, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B1=, C, D, E, and mixtures thereof; incorporating a second therapeutically active agent into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof; and bonding the gelatinous material to the substrate.
In accordance with another aspect of the present invention, there is provided use of a body protection article for reducing the discoloration and the thickness of keloid and hypertrophic scars.
-3a-These and other aspects of the present invention will become more apparent to those skilled in the art by reference to the following description and to the appended drawings.
BRIEF DESCRIPTION OF THE INVENTION
Fig. 1 is an elevational view of a glove according to the present invention.
Fig. 2 is a cross-sectional view along line 2-2 of Fig. 1.
Fig. 3 is an elevational view of a sock according to the present invention.
Fig. 4 is a cross-sectional view along line 4-4 of Fig. 3.
Figs. 5 and 6 are photographs showing a surgically repaired hand before and after contact with a gelatinous composition having an additive for treating the protected area.
DETAILED DESCRIPTION OF THE INVENTION
Figs. 1 to 4 show various embodiments of body protection articles constructed according to the principles of the present invention. Figs. 1 and 2 show a glove 10 and Figs. 3 and 4 illustrate a sock 12.
However, those skilled in the art will readily appreciate that the glove 10 and sock 12 shown are only exemplary, and many different articles worn on the body are useful for imparting a therapeutically active formulatio-n to the covered skin delivered from a gelatinous elastomeric composition according to the present invention. In a broader sense, however, a body protective article is provided in any shape and size required to cover a particular body part including shaped pads for use by women, men and children of all ages and sizes.
As shown in Figs. 1 and 2, the glove 10 is comprised of a palm piece 14 and a backhand piece 16, each a mirror image of the other. The palm piece 14 includes a wrist portion 18 extending across a palm portion 20 to four finger extensions 22 and a thumb extension 24. The back piece 16 of the glove similarly has a wrist portion 26 extending across a backhand portion 28 to form finger extensions 30 and a thumb extension (not shown). The palm piece 14 and the backhand piece 16 are joined together at their peripheral edges, such as by sewing, except at the respective wrist portions 18 and 26 providing an opening for putting a hand in the glove. A wrist piece 32 is folded over onto both sides of the palm piece 14 and the backhand piece 16 and sewn thereto surrounding the glove opening to prevent fraying and to add integrity for pulling the glove 10 onto a hand and for removing it therefrom.
The palm piece 14 and the backhand piece 16 are made from a cloth material having a gelatinous elastomeric composition 34 intimately bonded thereto.
The gelatinous composition 34 extends from a location spaced from the wrist piece 32, as shown by the dashed line 36, to the ends of the fingers 22, 30 and the thumb 24. Preferably the inner surface of the gelatinous composition closest to the human hand wearing the glove 10 directly contacts the skin.
The cloth material can be a knitted fabric constructed of both synthetic and natural yarns.
Suitable synthetic materials includes yarns such as SUBSTITUTE SHEET (RULE 26) polyester, polyamide such as nylon, polyolefin, acrylic and like fibers while suitable natural fibers include cotton, cambric, wool, cashmere, rayon, jute and others.
Figs. 3 and 4 show a sock 12 according to another embodiment of the present invention. The sock 12 is comprised of foot portion 50 leading to an ankle portion 52 extending to a lower leg portion 54. The sock 12 can be made having a generally tubular construction closed at one end by a toe portion 56 and seamed to provide a heel recess 58. In a similar manner as the glove 10, the sock 12 is made from a knitted cloth having a gelatinous elastomeric composition 60 intimately bonded thereto. The cloth and gelatinous composition of the sock 14 are selected from materials similar to those used to construct the respective palm and backhand pieces 14, 16 and the gelatinous composition 34 of the glove 10.
The gelatinous material preferably directly contacts the skin in a similar manner as shown and described with respect to the glove 10 to medicate the protected skin by means of a therapeutically active formulation as an additive incorporated therein. As shown in the cross-sectional view of Fig. 4, the gelatinous composition 60 extends from the toe portion 56 to the heel 58 and has a width sufficient to cover the bottom of the foot.
Suitable gelatinous compositions are prepared by melt blending an admixture comprising: about 1 part by weight of a high viscosity triblock copolymer of the general configurations poly(styrene-ethylene-butylene-styrene) (SEBS), poly(styrene-ethylene-propylene-styrene)(SEPS) or poly(styrene-ethylene-ethylene-propylene-styrene)(SEEPS), and from about 2 to about 15 parts by weight of a plasticizing oil. The block copolymer materials are commercially available from SUBSTITUTE SHEET (RULE 26) various sources including Shell under the Kraton designation, Kuraray Co., Ltd.
It will be understood that the block copolymer may comprise more complicated structures of either linear or branched configurations and may contain any desired number of polymer blocks as long as each of them has the identity and block molecular weights considered here. The block molecular weights employed for the present purpose are 5,000 to 75,000 average molecular weight in the monoalkylarene polymer blocks (preferably 8,000 to 65,000) and 25,000 to 250,000 average molecular weight for the hydrogenated blocks of conjugated dienes (preferably 35,000 to 110,000).
The block copolymers are characterized as having a Brookfield viscosity of a 20 weight percent solids solution of the block copolymer in toluene at 25 C. of about 1,800 cps and higher. Less typically, the Brookfield viscosity values of the block copolymer can range from about 1,800 cps to about 30,000 cps or higher.
Particularly preferred moderate to high viscosity SEPS and SEEPS block copolymers include Kuraray's 2006 and 4055 designations, which exhibit solution viscosities at 10 weight %, 30 C. of about 7.1 and 59, respectively, and styrene contents, by weight, of about 35% and 30%, respectively. For a more detailed description of block polymers that are useful with the present invention, reference is made to U.S. Patent No. 3,827,999 to Crossland. Recent reviews of triblock copolymers are found in the 'ENCYCLOPEDIA OF POLYMER SCIENCE
AND ENGINEERING", Volumes 2 and 5, 1987-1988; "'Thermoplastic Elastomers", MODERN PLASTIC ENCYCLOPEDIA, 1989; and Walker, B.M., Ed., et al., HANDBOOK OF THERMOPLASTIC ELASTOMERS, Van Nostrand Reinhold Co., 2nd Edition, 1988.
The gelatinous block materials are mixed with a - -- -------- -plasticizing oil to provide compositions that can be softened or melted at elevated temperatures but which regain elastomeric properties at ambient temperatures. Plasticizing oils particularly preferred for use in practicing the present invention are well known in the art. They include rubber processing oils such as paraffinic and naphthionic petroleum oils, highly refined aromatic-free paraffinic and naphthionic food and technical grade white petroleum mineral oils, and synthetic liquid oligomers of polybutene, polypropene, polyterpene, etc. The synthetic series process oils are high viscosity oligomers which are permanently fluid liquid nonolefins, isoparaffins or paraffins of moderate to high molecular weight. Examples of representative commercially available plasticizing oils include Amoco polybutenes, hydrogenated polybutenes and polybutenes with epoxide functionality at one end of the polybutene polymer and ARCO
Prime, Duraprime and Tufflo oils. Other white mineral oils include: Bayol , Bernol, American, Blandol, Drakeol , Ervol, Gloria, Kaydol, Litetek, Lyondell's Duraprime series, Marcolrv, Parol, Peneteck, Primol"', Protol, Sonrex, and the like.
Generally, plasticizing oils with average molecular weights less than about 200 and greater than about 700 may also be used.
According to the present invention, an effective amount of a therapeutically active formulation comprising a vitamin additive is incorporated into the gelatinous/plasticizing oil mixture. The vitamin additive is selected from the group of Vitamins A, B121 C, D, E, and mixtures thereof. Preferably, the vitamin additive is present in the therapeutically active formulation at a concentration of, by weight percent, about 1% to about 10%. The present invention further contemplates that any one of a number of medical grade natural oils can be incorporated into the therapeutically active formulation which is subsequently added to the gelatinous/plasticizing oil mixture.
Suitable medical grade natural oils include grape seed oil, avocado oil, jojoba oil, canola oil, ceramides and aloe, and mixtures thereof. Preferably, the natural oil is present in the gelatinous elastomeric composition at a concentration of, by weight percent, about 5% to about 35%. After the therapeutically active formulation has been provided, it is admixed with the gelatinous material/plasticizing oil in a range of, by weight, about 5% to about 50%. In some formulations, the natural oils can be used in lieu of the plasticizing oil to provide the resulting composition having the desired vicosity. In that case, the therapeutically active formulation is added to the gelatinous material, by weight, up to about 80%.
The gelatinous elastomeric composition can also contain useful amounts of conventionally employed additives such as stabilizers, antioxidants, antiblocking agents, colorants, fragrances, flame retardants, other polymers in minor amounts and the like to an extend not affecting or substantially decreasing the desired properties of the present invention.
The gelatinous elastomeric composition of the present invention may be made non-adhering, non-sticking, non-tacky by incorporating therein a suitable amount of one or more of a metal stearate selected from calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, and the like, and a suitable amount of one or more of a fatty amide selected from oleic acid, stearamide, behenamide, oleamide, erucamide, N,N"-ethylenebisstearamide, N,N"-ethylenebisoleamide, sterryl erucamide, erucyl erucamide, oleyl palmitamide, SUBSTITUTE SHEET (RULE 26) stearyl stearamide, erucyl stearamide, and the like, or a suitable wax selected from polyethylene, polypropylene, microcrystalline, carnauba, paraffin, montan, candelilla, beeswax, ozokerite, ceresine, and the like.
The gelatinous elastomeric compositions of the present invention are prepared by blending together the block copolymer, plasticizing oil and the therapeutically active formulation comprising the vitamin additive and preferably the natural oil components as desired at about 23 C. to about 1000 C., forming a paste like mixture and further heating the mixture to about 1500 C. to about 250 C. until a homogeneous molten blend is obtained. Lower and higher temperatures can also be utilized depending on the viscosity of the oils and amount of the block copolymer used. These components blend easily in the melt and a heated vessel equipped with a stirrer is all that is required.
An exemplary formulation for the therapeutically active component before incorporation into the gelatinous composition is as follows:
INGREDIENTS WEIGHT
Olive Oil 25.00 Canola Oil 25.00 Jojoba Oil Lite 25.00 Grape Seed Oil 12.00 N-stearyl phytosthingosine 10.00 SoyBean Extract Vitamin E Acetate 2.00 Fragrance 0.80 Di-tert-butyl-t-cresol 0.20 (Food Grade) Thus, the present invention body protection articles are formed from a molten blend of the gelatinous elastomeric material, plasticizing oil and the therapeutically active formulation comprising the SUBSTITUTE SHEET (RULE 26) vitamin additive, and optionally at least one of the enumerated natural oils intimately bonded to a cloth, fabric, paper or a polymeric film substrate by blending, melting, dipping, casting, injection molding, extruding and other conventional methods. For example, a preselected rigidity of a molten gelatinous elastomer composition is cast directly onto a cloth material to form the body protection article such as glove 10 and sock 12. The gelatinous elastomer composition can also be die cast, cut to size and heat bonded to the substrate. Likewise, a substrate such as of a cloth, paper, or a polymeric film material can be dipped into a preselected rigidity of a molten gelatinous elastomer composition and re-dipped into the same or different composition of a different rigidity. The shaped composite article of the invention can be conventionally covered with protective skins of elastomeric film, paper, cloth, fabric or combinations thereof, as needed.
Such a gelatinous elastomeric composition contacted to a surgical incision on a hand by means of a glove according to the present invention results in reduced scarring to the extent that after treatment, the area of an incision is nearly of the same texture and elasticity as that of undamaged skin. Figs. 5 and 6 are respective photographs showing a hand before contact with a gelatinous composition according to the present invention comprising a SEEPS block copolymer, plasticizing oil and the exemplary therapeutically active formulation set forth above, and about 42 days after contact with the composition of the present invention by means of glove 10. It is believed that the gelatinous elastomeric material serves as an occlusive blanket for "driving" the vitamin and natural oil additives into the skin. In that manner, the medical grade natural oil slowly dissipates from the gelatinous material onto the skin or scar to moisturize and SUBSTITUTE SHEET (RULE 26) lubricate the affected area. This is particularly advantageous for reducing the discoloration and thickness of both new and old keloid and hypertrophic scars in addition to improving the elasticity of the skin. The present invention can also be practiced in the form of shaped pads for treating facial conditions such as blemishes, liver spots, wrinkles and the like.
Many other therapeutic agents can be incorporated into the gelatinous elastomeric compositions of the present invention. For example, antifungal agents (fungal agents) such as ciclopirox, chloroxylenol, undecylenic acid, tolnaftate, miconizole, clotrizole, griseofulvin, and ketoconozole may be incorporated therein. Antibiotic agents such as mupirocin, erythromycin, gentimycin, neomycin, polymyxin, bacitracin, tetracyclines, and the like may also be incorporated into the gelatinous composition.
Antiseptic agents such as iodine, povidone-iodine, benzalkonium chloride, benzoic acid, chlorhexidine, nitrofurazone, benzoyl peroxide, hexachlorophene, phenol, resorcinol, and cetylpyridinium chloride likewise could be incorporated into the present invention. Furthermore, anti-inflammatories such as hydrocortisone, prednisone, triamcilolone, betamethasone and the like may be incorporated into the gelatinous composition. Still further, local anesthetics such as benzocaine, lidocaine, procaine, bupivicaine, a eutectic mixture of prilocaine and lignocaine, phenol, diphenhydramine, or the like may also be incorporated into the gelatinous composition. Additional agents that could be incorporated include penetration enhancers such as dimethyl sulfoxide or octolyphenylpolyethelene glycol, keratolytic agents such as salicylic acid, enzymes such as proteases and nucleases, hormones such as insulin, vesicants such as cantharadin, caustics such SUBSTITUTE SHEET (RULE 26) as podophyllin, and a myriad of additional pharmacologically active substances.
It is appreciated that various modifications to the inventive concepts described herein may be apparent to those of ordinary skill in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
SUBSTITUTE SHEET (RULE 26)
5,167,649; 5,181,914; and 5,330,452, all to Zook describe various devices comprising a viscoelastic gel pad having pharmacologically active agents incorporated into the gel. U.S. Patent No. 4,842,931 to Zook describes a pad made from a soft viscoelastic gel material containing a high percentage of plasticizing oil for equalizing pressure directed to corns, calluses, bunions and the like. It is also known to apply medication to the skin for the purpose of treating dermal afflictions and for delivering medicine to the body through the dermis. An example of such an externally applied rnedication is disclosed in U.S.
Patent No. 4,879,274 to Kamiya et al. which describes creams, ointments and the like comprising an a-monoglyceryl ether, a physiologically active material and an oily material. The physiologically active material comprises compounds such as drugs, growth hormones and the like including vitamins, for example, Vitamins A and Bõ .
However, what is needed is a body protection article such as a glove, socks, shaped pad and the like that is comprised of a therapeutically active formulation-containing gelatinous composition that imparts beneficial properties to the skin protected by the article. Such benefits include, but are not limited to, reducing scar tissue from burned skin and skin healing from a surgical procedure by maintaining the skin in a moist and lubricated state, treatment of skin blemishes and providing gentle compression to cushion and help absorb shock forces directed to the body.
SUMMARY OF THE INVENTION
The body protection article according to the present invention comprises a thermoplastic, gelatinous elastomeric composition containing a therapeutically active formulation as an additive incorporated therein.
When the gelatinous composition is intimately combined with a substrate such as a cloth material, paper or a polymeric film provided as a piece of clothing or a shaped pad sized to cover a particular part of the body, the therapeutically active formulation is released from the gel to affect the well-being of the person wearing the article. The gelatinous composition is preferable a block copolymer of the general configuration poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-propylene-styrene) and poly(styrene-ethylene-ethylene-propylene-styrene) combined within a plasticizing oil. Preferred therapeutically active SUBSTITUTE SHEET (RULE 26) formulation includes vitamin and/or natural oil additives.
In accordance with one aspect of the present invention, there is provided a body protection article, which comprises:
a substrate; a gelatinous material comprising a block polymer intimately bonded to the substrate; a first therapeutically active agent incorporated into the gelatinous material, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B121 C, D, E, and mixtures thereof; and a second therapeutically active agent incorporated into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof.
In accordance with another aspect of the present invention, there is provided a method for providing a body protection article, comprising the steps of: providing a substrate; incorporating a first therapeutically active agent into a gelatinous material comprising a block polymer, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B1=, C, D, E, and mixtures thereof; incorporating a second therapeutically active agent into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof; and bonding the gelatinous material to the substrate.
In accordance with another aspect of the present invention, there is provided use of a body protection article for reducing the discoloration and the thickness of keloid and hypertrophic scars.
-3a-These and other aspects of the present invention will become more apparent to those skilled in the art by reference to the following description and to the appended drawings.
BRIEF DESCRIPTION OF THE INVENTION
Fig. 1 is an elevational view of a glove according to the present invention.
Fig. 2 is a cross-sectional view along line 2-2 of Fig. 1.
Fig. 3 is an elevational view of a sock according to the present invention.
Fig. 4 is a cross-sectional view along line 4-4 of Fig. 3.
Figs. 5 and 6 are photographs showing a surgically repaired hand before and after contact with a gelatinous composition having an additive for treating the protected area.
DETAILED DESCRIPTION OF THE INVENTION
Figs. 1 to 4 show various embodiments of body protection articles constructed according to the principles of the present invention. Figs. 1 and 2 show a glove 10 and Figs. 3 and 4 illustrate a sock 12.
However, those skilled in the art will readily appreciate that the glove 10 and sock 12 shown are only exemplary, and many different articles worn on the body are useful for imparting a therapeutically active formulatio-n to the covered skin delivered from a gelatinous elastomeric composition according to the present invention. In a broader sense, however, a body protective article is provided in any shape and size required to cover a particular body part including shaped pads for use by women, men and children of all ages and sizes.
As shown in Figs. 1 and 2, the glove 10 is comprised of a palm piece 14 and a backhand piece 16, each a mirror image of the other. The palm piece 14 includes a wrist portion 18 extending across a palm portion 20 to four finger extensions 22 and a thumb extension 24. The back piece 16 of the glove similarly has a wrist portion 26 extending across a backhand portion 28 to form finger extensions 30 and a thumb extension (not shown). The palm piece 14 and the backhand piece 16 are joined together at their peripheral edges, such as by sewing, except at the respective wrist portions 18 and 26 providing an opening for putting a hand in the glove. A wrist piece 32 is folded over onto both sides of the palm piece 14 and the backhand piece 16 and sewn thereto surrounding the glove opening to prevent fraying and to add integrity for pulling the glove 10 onto a hand and for removing it therefrom.
The palm piece 14 and the backhand piece 16 are made from a cloth material having a gelatinous elastomeric composition 34 intimately bonded thereto.
The gelatinous composition 34 extends from a location spaced from the wrist piece 32, as shown by the dashed line 36, to the ends of the fingers 22, 30 and the thumb 24. Preferably the inner surface of the gelatinous composition closest to the human hand wearing the glove 10 directly contacts the skin.
The cloth material can be a knitted fabric constructed of both synthetic and natural yarns.
Suitable synthetic materials includes yarns such as SUBSTITUTE SHEET (RULE 26) polyester, polyamide such as nylon, polyolefin, acrylic and like fibers while suitable natural fibers include cotton, cambric, wool, cashmere, rayon, jute and others.
Figs. 3 and 4 show a sock 12 according to another embodiment of the present invention. The sock 12 is comprised of foot portion 50 leading to an ankle portion 52 extending to a lower leg portion 54. The sock 12 can be made having a generally tubular construction closed at one end by a toe portion 56 and seamed to provide a heel recess 58. In a similar manner as the glove 10, the sock 12 is made from a knitted cloth having a gelatinous elastomeric composition 60 intimately bonded thereto. The cloth and gelatinous composition of the sock 14 are selected from materials similar to those used to construct the respective palm and backhand pieces 14, 16 and the gelatinous composition 34 of the glove 10.
The gelatinous material preferably directly contacts the skin in a similar manner as shown and described with respect to the glove 10 to medicate the protected skin by means of a therapeutically active formulation as an additive incorporated therein. As shown in the cross-sectional view of Fig. 4, the gelatinous composition 60 extends from the toe portion 56 to the heel 58 and has a width sufficient to cover the bottom of the foot.
Suitable gelatinous compositions are prepared by melt blending an admixture comprising: about 1 part by weight of a high viscosity triblock copolymer of the general configurations poly(styrene-ethylene-butylene-styrene) (SEBS), poly(styrene-ethylene-propylene-styrene)(SEPS) or poly(styrene-ethylene-ethylene-propylene-styrene)(SEEPS), and from about 2 to about 15 parts by weight of a plasticizing oil. The block copolymer materials are commercially available from SUBSTITUTE SHEET (RULE 26) various sources including Shell under the Kraton designation, Kuraray Co., Ltd.
It will be understood that the block copolymer may comprise more complicated structures of either linear or branched configurations and may contain any desired number of polymer blocks as long as each of them has the identity and block molecular weights considered here. The block molecular weights employed for the present purpose are 5,000 to 75,000 average molecular weight in the monoalkylarene polymer blocks (preferably 8,000 to 65,000) and 25,000 to 250,000 average molecular weight for the hydrogenated blocks of conjugated dienes (preferably 35,000 to 110,000).
The block copolymers are characterized as having a Brookfield viscosity of a 20 weight percent solids solution of the block copolymer in toluene at 25 C. of about 1,800 cps and higher. Less typically, the Brookfield viscosity values of the block copolymer can range from about 1,800 cps to about 30,000 cps or higher.
Particularly preferred moderate to high viscosity SEPS and SEEPS block copolymers include Kuraray's 2006 and 4055 designations, which exhibit solution viscosities at 10 weight %, 30 C. of about 7.1 and 59, respectively, and styrene contents, by weight, of about 35% and 30%, respectively. For a more detailed description of block polymers that are useful with the present invention, reference is made to U.S. Patent No. 3,827,999 to Crossland. Recent reviews of triblock copolymers are found in the 'ENCYCLOPEDIA OF POLYMER SCIENCE
AND ENGINEERING", Volumes 2 and 5, 1987-1988; "'Thermoplastic Elastomers", MODERN PLASTIC ENCYCLOPEDIA, 1989; and Walker, B.M., Ed., et al., HANDBOOK OF THERMOPLASTIC ELASTOMERS, Van Nostrand Reinhold Co., 2nd Edition, 1988.
The gelatinous block materials are mixed with a - -- -------- -plasticizing oil to provide compositions that can be softened or melted at elevated temperatures but which regain elastomeric properties at ambient temperatures. Plasticizing oils particularly preferred for use in practicing the present invention are well known in the art. They include rubber processing oils such as paraffinic and naphthionic petroleum oils, highly refined aromatic-free paraffinic and naphthionic food and technical grade white petroleum mineral oils, and synthetic liquid oligomers of polybutene, polypropene, polyterpene, etc. The synthetic series process oils are high viscosity oligomers which are permanently fluid liquid nonolefins, isoparaffins or paraffins of moderate to high molecular weight. Examples of representative commercially available plasticizing oils include Amoco polybutenes, hydrogenated polybutenes and polybutenes with epoxide functionality at one end of the polybutene polymer and ARCO
Prime, Duraprime and Tufflo oils. Other white mineral oils include: Bayol , Bernol, American, Blandol, Drakeol , Ervol, Gloria, Kaydol, Litetek, Lyondell's Duraprime series, Marcolrv, Parol, Peneteck, Primol"', Protol, Sonrex, and the like.
Generally, plasticizing oils with average molecular weights less than about 200 and greater than about 700 may also be used.
According to the present invention, an effective amount of a therapeutically active formulation comprising a vitamin additive is incorporated into the gelatinous/plasticizing oil mixture. The vitamin additive is selected from the group of Vitamins A, B121 C, D, E, and mixtures thereof. Preferably, the vitamin additive is present in the therapeutically active formulation at a concentration of, by weight percent, about 1% to about 10%. The present invention further contemplates that any one of a number of medical grade natural oils can be incorporated into the therapeutically active formulation which is subsequently added to the gelatinous/plasticizing oil mixture.
Suitable medical grade natural oils include grape seed oil, avocado oil, jojoba oil, canola oil, ceramides and aloe, and mixtures thereof. Preferably, the natural oil is present in the gelatinous elastomeric composition at a concentration of, by weight percent, about 5% to about 35%. After the therapeutically active formulation has been provided, it is admixed with the gelatinous material/plasticizing oil in a range of, by weight, about 5% to about 50%. In some formulations, the natural oils can be used in lieu of the plasticizing oil to provide the resulting composition having the desired vicosity. In that case, the therapeutically active formulation is added to the gelatinous material, by weight, up to about 80%.
The gelatinous elastomeric composition can also contain useful amounts of conventionally employed additives such as stabilizers, antioxidants, antiblocking agents, colorants, fragrances, flame retardants, other polymers in minor amounts and the like to an extend not affecting or substantially decreasing the desired properties of the present invention.
The gelatinous elastomeric composition of the present invention may be made non-adhering, non-sticking, non-tacky by incorporating therein a suitable amount of one or more of a metal stearate selected from calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, and the like, and a suitable amount of one or more of a fatty amide selected from oleic acid, stearamide, behenamide, oleamide, erucamide, N,N"-ethylenebisstearamide, N,N"-ethylenebisoleamide, sterryl erucamide, erucyl erucamide, oleyl palmitamide, SUBSTITUTE SHEET (RULE 26) stearyl stearamide, erucyl stearamide, and the like, or a suitable wax selected from polyethylene, polypropylene, microcrystalline, carnauba, paraffin, montan, candelilla, beeswax, ozokerite, ceresine, and the like.
The gelatinous elastomeric compositions of the present invention are prepared by blending together the block copolymer, plasticizing oil and the therapeutically active formulation comprising the vitamin additive and preferably the natural oil components as desired at about 23 C. to about 1000 C., forming a paste like mixture and further heating the mixture to about 1500 C. to about 250 C. until a homogeneous molten blend is obtained. Lower and higher temperatures can also be utilized depending on the viscosity of the oils and amount of the block copolymer used. These components blend easily in the melt and a heated vessel equipped with a stirrer is all that is required.
An exemplary formulation for the therapeutically active component before incorporation into the gelatinous composition is as follows:
INGREDIENTS WEIGHT
Olive Oil 25.00 Canola Oil 25.00 Jojoba Oil Lite 25.00 Grape Seed Oil 12.00 N-stearyl phytosthingosine 10.00 SoyBean Extract Vitamin E Acetate 2.00 Fragrance 0.80 Di-tert-butyl-t-cresol 0.20 (Food Grade) Thus, the present invention body protection articles are formed from a molten blend of the gelatinous elastomeric material, plasticizing oil and the therapeutically active formulation comprising the SUBSTITUTE SHEET (RULE 26) vitamin additive, and optionally at least one of the enumerated natural oils intimately bonded to a cloth, fabric, paper or a polymeric film substrate by blending, melting, dipping, casting, injection molding, extruding and other conventional methods. For example, a preselected rigidity of a molten gelatinous elastomer composition is cast directly onto a cloth material to form the body protection article such as glove 10 and sock 12. The gelatinous elastomer composition can also be die cast, cut to size and heat bonded to the substrate. Likewise, a substrate such as of a cloth, paper, or a polymeric film material can be dipped into a preselected rigidity of a molten gelatinous elastomer composition and re-dipped into the same or different composition of a different rigidity. The shaped composite article of the invention can be conventionally covered with protective skins of elastomeric film, paper, cloth, fabric or combinations thereof, as needed.
Such a gelatinous elastomeric composition contacted to a surgical incision on a hand by means of a glove according to the present invention results in reduced scarring to the extent that after treatment, the area of an incision is nearly of the same texture and elasticity as that of undamaged skin. Figs. 5 and 6 are respective photographs showing a hand before contact with a gelatinous composition according to the present invention comprising a SEEPS block copolymer, plasticizing oil and the exemplary therapeutically active formulation set forth above, and about 42 days after contact with the composition of the present invention by means of glove 10. It is believed that the gelatinous elastomeric material serves as an occlusive blanket for "driving" the vitamin and natural oil additives into the skin. In that manner, the medical grade natural oil slowly dissipates from the gelatinous material onto the skin or scar to moisturize and SUBSTITUTE SHEET (RULE 26) lubricate the affected area. This is particularly advantageous for reducing the discoloration and thickness of both new and old keloid and hypertrophic scars in addition to improving the elasticity of the skin. The present invention can also be practiced in the form of shaped pads for treating facial conditions such as blemishes, liver spots, wrinkles and the like.
Many other therapeutic agents can be incorporated into the gelatinous elastomeric compositions of the present invention. For example, antifungal agents (fungal agents) such as ciclopirox, chloroxylenol, undecylenic acid, tolnaftate, miconizole, clotrizole, griseofulvin, and ketoconozole may be incorporated therein. Antibiotic agents such as mupirocin, erythromycin, gentimycin, neomycin, polymyxin, bacitracin, tetracyclines, and the like may also be incorporated into the gelatinous composition.
Antiseptic agents such as iodine, povidone-iodine, benzalkonium chloride, benzoic acid, chlorhexidine, nitrofurazone, benzoyl peroxide, hexachlorophene, phenol, resorcinol, and cetylpyridinium chloride likewise could be incorporated into the present invention. Furthermore, anti-inflammatories such as hydrocortisone, prednisone, triamcilolone, betamethasone and the like may be incorporated into the gelatinous composition. Still further, local anesthetics such as benzocaine, lidocaine, procaine, bupivicaine, a eutectic mixture of prilocaine and lignocaine, phenol, diphenhydramine, or the like may also be incorporated into the gelatinous composition. Additional agents that could be incorporated include penetration enhancers such as dimethyl sulfoxide or octolyphenylpolyethelene glycol, keratolytic agents such as salicylic acid, enzymes such as proteases and nucleases, hormones such as insulin, vesicants such as cantharadin, caustics such SUBSTITUTE SHEET (RULE 26) as podophyllin, and a myriad of additional pharmacologically active substances.
It is appreciated that various modifications to the inventive concepts described herein may be apparent to those of ordinary skill in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
SUBSTITUTE SHEET (RULE 26)
Claims (31)
1. A body protection article, which comprises:
a) a substrate;
b) a gelatinous material comprising a block polymer intimately bonded to the substrate;
c) a first therapeutically active agent incorporated into the gelatinous material, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B12, C, D, E, and mixtures thereof;
and d) a second therapeutically active agent incorporated into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof.
a) a substrate;
b) a gelatinous material comprising a block polymer intimately bonded to the substrate;
c) a first therapeutically active agent incorporated into the gelatinous material, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B12, C, D, E, and mixtures thereof;
and d) a second therapeutically active agent incorporated into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof.
2. The body protection article of claim 1 wherein the gelatinous material is selected from the group consisting of SEBS, SEPS, SEEPS, and mixtures thereof.
3. The body protection article of claim 1 wherein the substrate is selected from the group consisting of cloth, paper, a polymeric film, and mixtures thereof.
4. The body protection article of claim 3 wherein the cloth is a synthetic material selected from the group consisting of polyester, polyamide, polyolefin, acrylic, rayon, and mixtures thereof.
5. The body protection article of claim 3 wherein the cloth is a natural material selected from the group consisting of cotton, cambric, wool, cashmere, jute, and mixtures thereof.
6. The body protection article of claim 1 selected from the group consisting of a glove, sock, brace for a knee, ankle and elbow, and a shaped pad.
7. The body protection article of claim 1 wherein the gelatinous material further includes a third agent selected from the group consisting of an antifungal agent, an antibiotic agent, an antiseptic agent, an anti-inflammatory agent, an anesthetic, a penetration enhancer, a keratolytic agent, an enzyme, a hormone and a caustic agent, and mixtures thereof.
8. A method for providing a body protection article, comprising the steps of:
a) providing a substrate;
b) incorporating a first therapeutically active agent into a gelatinous material comprising a block polymer, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B12, C, D, E, and mixtures thereof;
c) incorporating a second therapeutically active agent into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof;
and d) bonding the gelatinous material to the substrate.
a) providing a substrate;
b) incorporating a first therapeutically active agent into a gelatinous material comprising a block polymer, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B12, C, D, E, and mixtures thereof;
c) incorporating a second therapeutically active agent into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof;
and d) bonding the gelatinous material to the substrate.
9. The method of claim 8 including selecting the gelatinous material from the group consisting of SEBS, SEPS, SEEPS, and mixtures thereof.
10. The method of claim 8 including selecting the substrate from the group consisting of cloth, paper, a polymeric film, and mixtures thereof.
11. The method of claim 8 including providing the body protection article as one selected from the group consisting of a glove, a sock, a knee brace, an ankle brace, an elbow brace, and a shaped pad.
12. The method of claim 8 including providing the substrate as a cloth of materials selected from the group consisting of cotton, cambric, wool, cashmere, rayon, jute, polyester, polyamide, polyolefin, acrylic, and mixtures thereof.
13. The method of claim 8 wherein the gelatinous material is mixed with a plasticizing oil in a ratio of about 1:2 to 1:15 by weight.
14. The method of claim 8 wherein the gelatinous material is mixed with a plasticizing oil, the first therapeutically active agent and the second therapeutically active agent at a temperature of about 23°C. to about 250°C.
15. The method of claim 8 wherein the gelatinous material is mixed with a plasticizing oil, the first therapeutically active agent, and the second therapeutically active agent at a first temperature range of about 23°C. to about 100°C. to form a paste-like mixture, followed by a further heating at a second temperature range of about 150°C. to about 250°C.
16. The method of claim 8 wherein the gelatinous material is rendered non-adhering, non-sticking and non-tacky by incorporating therein a metal stearate, and at least one of a fatty amide and a wax.
17. A method for providing a body protection article, comprising the steps of:
a) providing a substrate;
b) incorporating a first therapeutically active agent into a gelatinous material comprising a block polymer, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B12, C, D, E, and mixtures thereof;
c) incorporating a second therapeutically active agent into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof;
d) bonding the gelatinous material to the substrate;
e) forming the substrate having the gelatinous material bonded thereto into the body protection article.
a) providing a substrate;
b) incorporating a first therapeutically active agent into a gelatinous material comprising a block polymer, wherein the first therapeutically active agent is selected from the group consisting of Vitamins A, B12, C, D, E, and mixtures thereof;
c) incorporating a second therapeutically active agent into the gelatinous material, wherein the second therapeutically active agent is a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, aloe, olive oil, and mixtures thereof;
d) bonding the gelatinous material to the substrate;
e) forming the substrate having the gelatinous material bonded thereto into the body protection article.
18. The method of claim 17 including selecting the gelatinous material from the group consisting of SEBS, SEPS, SEEPS, and mixtures thereof.
19. The method of claim 16 wherein the gelatinous material further includes a third agent selected from the group consisting of an antifungal agent, an antibiotic agent, an antiseptic agent, an anti-inflammatory agent, an anesthetic, a penetration enhancer, a keratolytic agent, an enzyme, a hormone and a caustic agent, and mixtures thereof.
20. The method of claim 17 including providing the body protection article as one selected from the group consisting of a glove, a sock, a knee brace, an ankle brace, an elbow brace, and a shaped pad.
21. The method of claim 17 including selecting the substrate from the group consisting of cloth, paper, a polymeric film, and mixtures thereof.
22. The method of claim 21 wherein the cloth is a synthetic material selected from the group consisting of rayon, polyester, polyamide, polyolefin, acrylic, and mixtures thereof.
23. The method of claim 21 wherein the cloth is a natural material selected from the group consisting of cotton, cambric, wool, cashmere, jute, and mixtures thereof.
24. The method of claim 17 wherein the gelatinous material is mixed with a plasticizing oil in a ratio of about 1:2 to 1:15 by weight.
25. The method of claim 17 wherein the gelatinous-material is mixed with a plasticizing oil, the first therapeutically active agent and the second therapeutically active agent at a temperature of about 23°C to about 250°C.
26. The method of claim 17 wherein the gelatinous material is mixed with a plasticizing oil, the first therapeutically active agent, and the second therapeutically active agent at a first temperature range of about 23°C. to about 100°C. to form a paste-like mixture, followed by a further heating at a second temperature range of about 150°C.
to about 250°C.
to about 250°C.
27. The method of claim 17 including rendering the gelatinous material non-adhering, non-sticking and non-tacky by incorporating therein a metal stearate, and at least one of a fatty amide and a wax.
28. A body protection article, which comprises:
a) a substrate;
b) a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, olive oil, aloe, and mixtures thereof;
c) a gelatinous material comprising a block polymer selected from the group consisting of SEBS, SEPS, SEEPS, and mixtures thereof, wherein the natural oil is incorporated into the block copolymer bonded to the substrate having a shape to cover a desired body portion; and d) a therapeutically active agent selected from the group consisting of Vitamins A, B12, C, D, and E, and mixtures thereof, incorporated into said gelatinous material.
a) a substrate;
b) a natural oil selected from the group consisting of grape seed oil, avocado oil, jojoba oil, canola oil, ceramides, olive oil, aloe, and mixtures thereof;
c) a gelatinous material comprising a block polymer selected from the group consisting of SEBS, SEPS, SEEPS, and mixtures thereof, wherein the natural oil is incorporated into the block copolymer bonded to the substrate having a shape to cover a desired body portion; and d) a therapeutically active agent selected from the group consisting of Vitamins A, B12, C, D, and E, and mixtures thereof, incorporated into said gelatinous material.
29. A body protection article, which comprises:
a) a substrate; and b) a block polymer having incorporated therein, by weight, about 25% olive oil, about 25% canola oil, about 25%
jojoba oil, about 12% grape seed oil, about 10% N-stearyl phylosthingosine soybean extract, about 2% vitamin E, remainder inert ingredients, wherein the substrate has a shape to cover a desired body portion.
a) a substrate; and b) a block polymer having incorporated therein, by weight, about 25% olive oil, about 25% canola oil, about 25%
jojoba oil, about 12% grape seed oil, about 10% N-stearyl phylosthingosine soybean extract, about 2% vitamin E, remainder inert ingredients, wherein the substrate has a shape to cover a desired body portion.
30. Use of the body protection article of any one of claims 17, 18 and 20 to 28 for reducing the discoloration and the thickness of keloid and hypertrophic scars.
31. Use of the body protection article of claim 17 for about 42 days for reducing the discoloration and the thickness of keloid and hypertrophic scars.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/143,282 | 1998-08-28 | ||
| US09/143,282 US6117119A (en) | 1998-08-28 | 1998-08-28 | Gelatinous body protection article having a therapeutic additive |
| PCT/US1999/018039 WO2000012170A1 (en) | 1998-08-28 | 1999-08-09 | Gelatinous body protection article having a therapeutic additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2341303A1 CA2341303A1 (en) | 2000-03-09 |
| CA2341303C true CA2341303C (en) | 2007-05-22 |
Family
ID=22503388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002341303A Expired - Fee Related CA2341303C (en) | 1998-08-28 | 1999-08-09 | Gelatinous body protection article having a therapeutic effect |
Country Status (14)
| Country | Link |
|---|---|
| US (2) | US6117119A (en) |
| EP (1) | EP1107812B1 (en) |
| JP (1) | JP2002523193A (en) |
| KR (1) | KR100418319B1 (en) |
| AR (1) | AR024510A1 (en) |
| AT (1) | ATE312642T1 (en) |
| AU (1) | AU743008B2 (en) |
| BR (1) | BR9913313B1 (en) |
| CA (1) | CA2341303C (en) |
| DE (1) | DE69928941T2 (en) |
| DK (1) | DK1107812T3 (en) |
| ES (1) | ES2252961T3 (en) |
| TW (1) | TW478940B (en) |
| WO (1) | WO2000012170A1 (en) |
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-
1998
- 1998-08-28 US US09/143,282 patent/US6117119A/en not_active Expired - Lifetime
-
1999
- 1999-08-09 DE DE69928941T patent/DE69928941T2/en not_active Expired - Lifetime
- 1999-08-09 AT AT99939717T patent/ATE312642T1/en active
- 1999-08-09 CA CA002341303A patent/CA2341303C/en not_active Expired - Fee Related
- 1999-08-09 JP JP2000567275A patent/JP2002523193A/en active Pending
- 1999-08-09 ES ES99939717T patent/ES2252961T3/en not_active Expired - Lifetime
- 1999-08-09 EP EP99939717A patent/EP1107812B1/en not_active Expired - Lifetime
- 1999-08-09 KR KR10-2001-7002563A patent/KR100418319B1/en not_active IP Right Cessation
- 1999-08-09 AU AU53957/99A patent/AU743008B2/en not_active Ceased
- 1999-08-09 DK DK99939717T patent/DK1107812T3/en active
- 1999-08-09 WO PCT/US1999/018039 patent/WO2000012170A1/en active IP Right Grant
- 1999-08-09 BR BRPI9913313-0A patent/BR9913313B1/en not_active IP Right Cessation
- 1999-08-27 AR ARP990104312A patent/AR024510A1/en unknown
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2000
- 2000-02-15 TW TW088114715A patent/TW478940B/en active
- 2000-09-01 US US09/654,581 patent/US6673054B1/en not_active Expired - Fee Related
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| AU5395799A (en) | 2000-03-21 |
| BR9913313A (en) | 2001-05-22 |
| ATE312642T1 (en) | 2005-12-15 |
| AU743008B2 (en) | 2002-01-17 |
| AR024510A1 (en) | 2002-10-16 |
| TW478940B (en) | 2002-03-11 |
| DE69928941T2 (en) | 2006-08-10 |
| ES2252961T3 (en) | 2006-05-16 |
| DE69928941D1 (en) | 2006-01-19 |
| BR9913313B1 (en) | 2008-11-18 |
| US6673054B1 (en) | 2004-01-06 |
| JP2002523193A (en) | 2002-07-30 |
| EP1107812A4 (en) | 2004-05-12 |
| EP1107812B1 (en) | 2005-12-14 |
| EP1107812A1 (en) | 2001-06-20 |
| KR20010079708A (en) | 2001-08-22 |
| DK1107812T3 (en) | 2006-04-18 |
| US6117119A (en) | 2000-09-12 |
| CA2341303A1 (en) | 2000-03-09 |
| KR100418319B1 (en) | 2004-02-11 |
| WO2000012170A1 (en) | 2000-03-09 |
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| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20140811 |