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Publication numberUSRE34682 E
Publication typeGrant
Application numberUS 08/016,806
Publication dateAug 2, 1994
Filing dateFeb 11, 1993
Priority dateJun 16, 1989
Fee statusPaid
Also published asCA2019117A1, CA2019117C, DE69028463D1, DE69028463T2, EP0413418A2, EP0413418A3, EP0413418B1, US4992508, USRE34716
Publication number016806, 08016806, US RE34682 E, US RE34682E, US-E-RE34682, USRE34682 E, USRE34682E
InventorsMohan Vishnupad, Jose Ramirez
Original AssigneeImaginative Research Associates, Inc.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Aqueous dispersions of polyester and polyesteramides cross-linked with metallic ions and casts made therefrom
US RE34682 E
Abstract
Cross-linked aqueous dispersions and emulsions and method for producing casts of any desirable shape therefrom the dispersions comprising a water dissipatable polymer in an amount from 18 to 30 percent by weight based on the total weight of the composition: water in an amount from .[.67 to 130.]. .Iadd.30-80 .Iaddend.percent by weight based on the total weight of the composition; a source of multivalent metallic ions in an amount of 0.1 to 5 percent by weight based on the total weight of the composition; and humectant in an amount from 0.1 to 40 percent by weight based on the total weight of the composition and the emulsions comprising a water dissipatable polymer in an amount from 18 to 30 percent by weight based on the total weight of the composition; water in an amount from .[.67.]. .Iadd.30 .Iaddend.to 80 percent by weight based on the total weight of the comosition; emollient oils in an amount from 0.1 to 25 percent by weight based on the total weight of the composition; a source of multivalent metallic ions in an amount from 0.1 to 5 percent by weight based on the total weight of the composition; humectants in an amount from 0.1 to 40 percent by weight based on the total weight of the composition; and emulsifier in an amount from 0.01 to 5 percent by weight based on the total weight of the composition.
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Claims(3)
What is claimed is:
1. A cross linked aqueous dispersion composition comprising:
a water dissipatable polymer in an amount from 18 to 30 percent by weight based on the total weight of the compositions;
water in an amount from .[.67.]. .Iadd.30 .Iaddend.to 80 by weight based on the total weight of the composition;
a source of multivalent metallic ions in an amount of 0.1 to 5 percent by weight on the total weight of the composition; and
humectant in an amount from 0.1 to 40 percent by weight based on the total weight of the composition.
2. A cross-linked dispersion composition according to claim 1 wherein said source of multivalent metallic ions is selected from the group consisting of magnesium chloride, zinc acetate, zinc gluconate, zinc oxide, titanium dioxide and magnesium acetate.
3. An article manufactured using the composition of claim 1.
Description
FIELD OF THE INVENTION

This invention relates generally to cross-linking an aqueous dispersion of polyester or polyesteramide with the water soluble multivalent metallic ions. The aqueous dispersion of polyester or polyesteramides containing ether and sulfonate groups can also contain humectants and/or emollients which when cross-linked with metallic ions and poured into any desirable shaped mold form a clear or opaque cast of therapeutic functional nature. This invention also relates to the process of cross-linking the polyester or polyesteramide aqueous dispersion with metallic ions.

BACKGROUND OF THE INVENTION

Many compositions used for skin treatment contain emollients of humectants in lotion, cream or gel form. Such products are applied by evenly spreading the product on the skin. Upon loss of water, the product dries providing humectants and emollients to the epidermis.

Water soluble gels that form protective films of various types are known. For example, U.S. Pat. No. 4,393,048 discloses a water soluble hydrogel of alkali metal alginate and glycerine that dries to a non-toxic, pliable protective film. U.S. Pat. No. 3,949,742 discloses a transparent medical dressing which performs as a synthetic film over skin wounds. Water soluble polyesters, for example U.S. Pat. No. 4,502,976, are used to form cross-linked bioerodible hydrogels. The hydrogels, suitable for carrying water soluble therapeutic macromolecules and for implantantion in living mammals, are produced by a complex polymerization process without using water soluble metallic ions.

U.S. Pat. No. 3,879,168 to Franklin discloses a surgical dressing made of partially soluble alginic materials in the form of gauze or wool characterized by a pH of 4 to 7 and a calcium content of 2-6% by weight comprised of a laminate of a thin layer of non-porous segmented polyurethane sewn to foam.

U.S. Pat. Nos. 3,734,874, 4,233,196, 4,335,220, 4,304,900, 4,304,901, and 4,300,580 describe water-dissipatable, meltable polyesters that are useful as adhesives, coating materials, films, packaging materials and other products that can be dissolved, dispersed or otherwise dissipated in water or aqueous solutions. These polyesters, however, are not cross-linked using metallic ions and cast into shapes to entrap water, humectants and/or emollients within the hardened cast.

As explained in a technical publication from Eastman, the water dispersability of the AQ polymer is largely attributed to the presence of ionic substituents attached to the polymer chain. A simplified representation of the polymer is shown below: ##STR1## wherein "A" is an aromatic dicarboxylic acid moiety some of which have sodiofulfo (--SO3 -, Na+) substituents, "G" is an aliphatic or cycloaliphatic glycol residue and "OH" is a hydroxy end group.

It is the sodio sulfo group which impart the water dispersability to the polymer. To cross-link with multivalent metallic ions and obtain the moldable shapes of this invention, the multivalent metal salts must be added and mixed according to the teaching of this invention. Departing from this process results in non-compatible mixtures of non-commercial properties. Eastman technical publications teach the synthesis and preferred methods for crosslinking water dispersible polyesters and polyesteramides with other resins through high temperature curing process and subsequent drying of the cured resins, but specifically warn against the use of the heavy metal salts included in this invention as being not compatable with the polymers used in this invention.

OBJECTS OF THE INVENTION

It is therefore an object of the present invention to provide novel cross-linked polyester polymers with humectants and/or emollients by using water soluble metallic ions.

A further object of the present invention is to provide a convenient process of cross-linking the humectant and emollients with the polyester polymer in the presence of water soluble metallic ions.

A further object of this invention is to provide such casted patches containing water soluble medicaments and oil soluble medicaments. Such patches can be used as controlled release transdermal delivery patches.

SUMMARY OF THE INVENTION

It has been found that the objectives of this invention may be realized by forming a cast containing humectants and/or emollient oils, water, water dissipatable polyesters, and by cross-linking with water soluble multivalent metal ions. Such compositions when poured into a mold harden without pressure and have utility in wound treatment, skin treatment and controlled release drug and fragrance patches.

The casts of this invention comprise water dissipatable polyester or polyesteramide in an amount from 18 to 30 percent by weight, water in an amount from .[.67.]. .Iadd.30 .Iaddend.to 80%, humectants in an amount from 0.01 to 40% by weight, and a source of multivalent metal ions for cross-linking purposes in an amount from 0.01 to 5 percent. Casts of this invention can also be formulated using emollient oils in an amount from 0.01 to 25% by weight based on the total weight of the composition, water dissipatable polyester in an amount from 18-30% by weight, water in an amount from .[.67.]..Iadd.30.Iaddend.-80% by weight based on the total weight of the composition, and a source of multivalent metallic ions in an amount from 0.01 to 5% based on the total weight of the composition. Optionally the composition also contains fragrance oils, medical agents or color.

DETAILED DESCRIPTION OF THE INVENTION

Cross-linked clear casts of the present invention comprise (a) a water dissipatable polyester polymer in an amount from 18-30% by weight based on the total weight of the composition; (b) water in an amount from .[.67.]..Iadd.30.Iaddend.-80% by weight based on the total weight of the composition; (c) a source of multivalent metallic ions in an amount of 0.1-5% by weight based on the total weight of the composition; (d) humectant such propylene glycol, glycerine in an amount from 0.1-40% by weight based on the total weight of the composition.

The cross-linked cast of the present invention can also be in the form of an opaque emulsion system. Such emulsion cast of the present invention comprise (a) a water dissipatable polymer in an amount from 18 to 30% by weight based on the total weight of the composition; (b) water in an amount from .[.67.]..Iadd.30.Iaddend. to 80% by weight based on the total weight of the composition; (c) emollient oils in an amount from 0.1 to 25% by weight based on the total weight of the composition; (d) a source of multivalent metallic ions in an amount from 0.1 to 5% by weight based on the total weight of the composition; (e) humectants in an amount from 0.01 to 40% by weight-based on the total weight of the composition; (f) any suitable oil-in-water emulsifier in an amount from 0.01 to 5% by weight based on the total weight of the composition.

Polymers useful in the present invention must be capable of cross-linking with water soluble metal ions, and, when poured in liquid from into a mold hardening without pressure to form a cast of any desirable shape. Polymers suitable for use in this invention include the water-dissipatable polyester and polyesteramides described in U.S. Pat. No. 3,734,874 to Kibler, et al., U.S. Pat. No. 4,233,196 to Sublet and U.S. Pat. No. 4,304,901 to O'Neill, et al. A preferred water dissipatable polyester is commercially available on Eastman AQ 55S polymers.

Examples of organic and inorganic sources of the multivalent metal ions used to cross-link the polymers in this invention include magnesium chloride, zinc acetate, zinc gluconate, zinc oxide, titanium dioxide, and magnesium acetate. The preferred sources of multivalent metal ions are water soluble and include zinc gluconate and magnesium chloride.

In forming the clear cross-linked casts of this invention, water by itself or in combination with humectant such as propylene glycol and glycerine may be used.

In forming cross-linked emulsion casts of this invention any emollient oil may be used. Emollients useful in this invention include hydrocarbon oils and semi-solid hydrocarbons, lanolin and derivatives, silicone oils and esters commonly used in the cosmetic and dermatological fields.

The cross-linking of polymer containing emulsion systems by means of multivalent metallic ions can be achieved with or without the additional emulsfiers. The selection of an appropriate emulsifier for a given system is within the purview of one skilled in the art.

Optionally, a wide variety of agents may be incorporated into the compositions of this invention for a variety of purposes. For example, medicaments such as benzoyl peroxide, methyl nicolinate, salicylic acid, benzocaine and methanol can be cast into desirable shapes for therapeutic use.

The cross-linked hydrogels and emulsions can be cast into any desirable shape and used for various purposes. For example, casts in the form of face masks may be used for treating dry skin. Casts in the form of patches or pads may be used to cover burns and wounds for soothing and comforting the inflamed area, or for delivering active medicaments to the damaged skin as a controlled release, transdermal patch.

Both the clear and opaque emollient casts may also contain fragrance, insect repellents, sun screens and like chemicals.

The following examples illustrate how the cross-linked casts of this invention may be formed.

EXAMPLE 1

A clear cross-linked cast was produced having the following composition:

______________________________________Eastman AQ 55S Polymer              24.0Zinc Gluconate (USP)               2.0Propylene Glycol   34.0Water              .[.42.0.]. .Iadd.40.Iaddend.______________________________________

The cross-linked cast of Example 1 was prepared by placing the appropriate amounts of water and propylene glycol into a suitable container and heating the mixture to 80° C. The appropriate amount of polymer was gradually added with a high shear mixing to dissolve the solids. When all the solids were added, high shear mixing is continued, until a clear, straw colored, thick gel was produced. The gel was then cooled to room temperature and an appropriate amount of zinc gluconate aqueous solution added by high shear mixture until cross-linking occurred. The liquid was poured into a mold of desirable shape to produce a cast of hydrogel. The metallic cross-linking can be done either at room temperature or at elevated temperatures depending on the composition.

EXAMPLE 2

An emulsion crosslinked cast was produced having the following composition:

______________________________________Eastman AQ 55S Polymer               20.3Propylene Glycol    28.0Mineral oil         10.0PJ                  7.0Polysorbate 20      1.0Zinc gluconate      2.0Water               31.7______________________________________

The cross-linked emulsion casts of Example 2 were formed by placing appropriate amounts of water and propylene glycol in a suitable container and heating the mixture to 80° C. The appropriate amount of polymer was gradually added with a high shear mixing until a clear viscous liquid was produced. The polysorbate 20 was added to the clear liquid and mixing continued. The melted oil phase was then added to the aqueous phase and homogenized to form a smooth emulsion. To this emulsion the appropriate amount of aqueous solution of znc gluconate was added with continued mixing. Pouring into a mold at appropriate viscosity formed a cast of the desired shape. The cross-linking of the emulsion can be carried out between 50° C., to 70° C., as desired, for manufacturing and suitable for pouring into the molds for casting purposes.

EXAMPLE 3

Water insoluble sources of multivalent metallic ions such as, for example, zinc oxide or titanium dioxide can be added to form more rigid cross-linked casts.

______________________________________Eastman AQ55S Polymer                21.00Propylene Glycol     28.00Petroleum Jelly      15.00Glycerol Monostearate and                1.00Polyoxyethylene stearateZinc Oxide           2.00Zinc Gluconate       2.00Microcrystalline Wax 5.00Water                26.00______________________________________
EXAMPLES 4-24

The following are additional specific examples of formulations used to produce cross-linked casts of this invention:

______________________________________Ex. 4Eastman AQ 55S polymer              21Propylene glycol   28Zinc gluconate     2Water              49Ex. 5Eastman AQ 55S polymer              25.5Propylene glycol   34.0Zinc gluconate     2.0Water              38.5Ex. 6Eastman AQ 55S polymer              20.3Propylene glycol   18.0Zinc gluconate     2.0Water              59.7Ex. 7Eastman AQ 55S polymer              23.2Propylene glycol   10.0Zinc gluconate     2.0Water              64.8Ex. 8Eastman AQ 55S polymer              21Propylene glycol   28Zinc gluconate     2Water              49Ex. 9Eastman AQ 55S polymer              24Propylene glycol   32Zinc gluconate     2Water              42Ex. 10Eastman AQ 55S polymer              27Propylene glycol   36Zinc gluconate     2Water              35Ex. 11Eastman AQ 55S polymer              23.2Zinc gluconate     2.0Water              74.8Ex. 12Eastman AQ 55S polymer              23.2Magnesium chloride 0.5Water              76.3Ex. 13Eastman AQ 55S polymer              24Glycerine          32Zinc gluconate     2Water              42Ex. 14Eastman AQ 55S polymer              24.0Propylene glycol   32.0Magnesium chloride 0.3Water              43.7Ex. 15Eastman AQ 29S polymer              15.0Eastman AQ 55S polymer              5.4Propylene glycol   27.2Mineral oil        10.0Polysorbate 20     2.0Zinc gluconate     3.0Water              37.4Ex. 16Eastman AQ 55S polymer              20.3Propylene glycol   28.0Mineral oil        10.0Petroleum jelly    7.0Polysorbate 20     1.0Zinc gluconate     2.0Water              31.7Ex. 17Eastman AQ 55S polymer              20.3Propylene glycol   28.0Mineral oil        10.0Petroleum jelly    7.0Polysorbate 20     1.0Zinc gluconate     1.5Water              32.2Ex. 18Eastman AQ 55S polymer              18.0Propylene glycol   24.0Petroleum jelly    17.0Polysorbate 20     1.0Zinc gluconate     2.0Water              38.0Ex. 19Eastman AQ 55S polymer              21Propylene glycol   28Dimethicone        .[.19.]. .Iadd.9 .Iaddend.Petroleum jelly    9Glycerolmonostearate              1and PolyoxyethyleneStearateZinc gluconate     2Water              30Ex. 20Eastman AQ 55S polymer              21.0Propylene glycol   28.0Petroleum jelly    17.0Zinc gluconate     2.0Water              32.0Ex. 21Eastman AQ 55S polymer              21.0Propylene glycol   28.0Petroleum jelly    16.0Salicylic acid     2.0Zinc gluconate     2.0Water              .[.10.0.]. .Iadd.31.0.Iaddend.Ex. 22Eastman AQ 55S polymer              20.7Propylene glycol   27.6Petroleum jelly    15.0Benzoyl peroxide   2.0Glycerine          2.0Zinc gluconate     2.0Water              30.7Ex. 23Eastman AQ 55S polymer              21.0Propylene glycol   28.0Menthol            2.0Zinc gluconate     2.0Water              .[.26.0.]. .Iadd.47.0.Iaddend.Ex. 24Eastman AQ 55S polymer              21.0Propylene glycol   28.0Petroleum jelly    15.0Polysorbate 20     1.0Superabsorbant polymer              1.0Zinc gluconate     1.0Water              33.0______________________________________

Although particular illustrative embodiments of the present invention have been described herein, the present invention is not limited to these particular embodiments. Various changes and modifications may be made thereto by those skilled in the art without departing from the spirit or scope of the invention, which is defined in the appended claims.

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Non-Patent Citations
Reference
1"Eastman AQ™ Polymer-A Unique Dispersant For Hydrophobic Materials" by Michael J. Idacavage dated Dec. 1987.
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6960748Oct 9, 2003Nov 1, 2005Smurfit-Stone Container Enterprises, Inc.six-sided box with side panels and expandable charge pouch adhered to bottom; tabs for safe removal when hot; substantially leak resistant corners; suitable for shipping, storage, cooking, and consumption of popcorn
Classifications
U.S. Classification524/601, 524/783, 524/608, 524/764, 524/605, 524/763, 524/755, 528/272, 528/282, 524/602, 528/275, 528/281, 524/767
International ClassificationA61K9/70, A61K8/85, C08J3/24, A61Q19/00, C08K5/098, C08K3/00, A61K8/02, C08K3/22, A61K8/27
Cooperative ClassificationA61K8/0212, A61Q19/00, C08J3/24, A61K8/27, C08K3/22, A61K9/7023, C08K3/0075, C08K3/0016, A61K8/85, C08K5/098
European ClassificationC08K3/00S, C08K5/098, C08K3/22, A61K8/85, C08K3/00P2, C08J3/24, A61K9/70E, A61K8/02F, A61K8/27, A61Q19/00
Legal Events
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Aug 12, 2002FPAYFee payment
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