USRE34716E - Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom - Google Patents

Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom Download PDF

Info

Publication number
USRE34716E
USRE34716E US08/016,808 US1680893A USRE34716E US RE34716 E USRE34716 E US RE34716E US 1680893 A US1680893 A US 1680893A US RE34716 E USRE34716 E US RE34716E
Authority
US
United States
Prior art keywords
composition
amount
water
percent
total weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US08/016,808
Inventor
Mohan Vishnupad
Jose Ramirez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PEOPLE'S BANK
Original Assignee
Imaginative Research Associates Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/652,233 external-priority patent/US5110862A/en
Application filed by Imaginative Research Associates Inc filed Critical Imaginative Research Associates Inc
Priority to US08/016,808 priority Critical patent/USRE34716E/en
Application granted granted Critical
Publication of USRE34716E publication Critical patent/USRE34716E/en
Assigned to PEOPLE'S BANK reassignment PEOPLE'S BANK ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IMAGINATIVE RESEARCH ASSOCIATES, INC.
Assigned to IMAGINATIVE RESEARCH ASSOCIATES, INC. reassignment IMAGINATIVE RESEARCH ASSOCIATES, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: CONNECTICUT DEVELOPMENT AUTHORITY
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212Face masks
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85Polyesters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/70Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • A61K9/7023Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/011Crosslinking or vulcanising agents, e.g. accelerators
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/10Metal compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals

Definitions

  • 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.
  • compositions used for skin treatment contain emollients or humectants in lotion, cream or gel form. Such product 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.
  • 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 implantation 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, metalable 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.
  • 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.
  • 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 int a mold harden without pressure and have utility in wound treatment, skin treatments and controlled release drug and fragrance patches.
  • the casts of this invention comprise water dissipatable polyester or polyesteramide in an amount from 18 to 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 crosslinking 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 15% 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.].
  • the composition also contains fragrance oils, medical agents or color.
  • 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 as 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.
  • 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 am amount from .[.67.].
  • emollient oils in an amount from 0.1 to 25% by weight based on the total weight of the composition
  • a source of multivalent metallic ions in an amount from 0.1 to 5% by weight based on the total weight of the composition
  • humectants in an amount from 0.01 to 40% by weight based on the total weight of the composition
  • 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 form 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 5S polymers.
  • 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.
  • water by itself or in combination with humectant such as propylene glycol and glycerine may be used.
  • Emollient oil 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.
  • cross-linking of polymer containing emulsion systems by means of multivalent metallic ions can be achieved with or without the additional emulsifiers.
  • the selection of an appropriate emulsifier for a given system is within the purview of one skilled in the art.
  • agents may be incorporated into the compositions of this invention for a variety of purposes.
  • medicaments such as benzoyl peroxide, methyl nicolinate, salicyclic acid, benzocaine and menthol can be cast into desirable shapes for therapeutic use.
  • the cross-linked hydrogels and emulsions can be cast into any desirable shape and sued for various purposes.
  • casts in the form of face masks may be used for treating dry skin.
  • Casts in the form of patches or pads may be sued 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, such screens and like chemicals.
  • a clear cross-linked cast was produced having the following composition:
  • 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 solid 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 mixing 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.
  • An emulsion crosslinked cast was produced having the following composition:
  • Polysorbate 20 1.0
  • 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 as then added to the aqueous phase and homogenized to form a smooth emulsion. To this emulsion the appropriate amount of aqueous solution of zinc 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.
  • 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.
  • Microcrystalline Wax 5.00
  • Polysorbate 20 1.0
  • Polysorbate 20 1.0
  • Polysorbate 20 1.0
  • Polysorbate 20 1.0
  • Zinc gluconate 1.0

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 30.]. .Iadd.30 to 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 composition; 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 am 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 am amount from 0.01 to 5 percent by weight based on the total weight of the composition.

Description

This is a continuation, of copending application Ser. No. 07/578,018 filed on Sep. 5, 1990, now abandoned, which is a divisional of co-pending application Ser. No. 07/367,183 filed Jun. 16, 1989, now U.S. Pat. No. 4,992,508.
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 or humectants in lotion, cream or gel form. Such product 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 implantation 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, metalable 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 metals salts must be added and mixed according to the teaching of this invention. Departing from this process results in non-compatible mixtures of non-commerical 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 compatible 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 int a mold harden without pressure and have utility in wound treatment, skin treatments and controlled release drug and fragrance patches.
The casts of this invention comprise water dissipatable polyester or polyesteramide in an amount from 18 to 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 crosslinking 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 15% 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 am 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 as 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 am 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 form 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 5S 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 emulsifiers. 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, salicyclic acid, benzocaine and menthol can be cast into desirable shapes for therapeutic use.
The cross-linked hydrogels and emulsions can be cast into any desirable shape and sued 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 sued 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, such screens and like chemicals.
The following examples illustrate how the crosslinked casts of this invention may be formed.
EXAMPLE 1
A clear cross-linked cast was produced having the following composition:
Eastman at 55S Polymer: 24.0
Zinc Gluconate (USP): 2.0
Propylene Glcyol: 34.0
Water: .[.42.0.]. .Iadd.40.0 .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 solid 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 mixing 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: 20.3
Propylene Glycol: 28.0
Mineral oil: 10.0
PJ: 7.0
Polysorbate 20: 1.0
Zinc gluconate: 2.0
Water: 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 as then added to the aqueous phase and homogenized to form a smooth emulsion. To this emulsion the appropriate amount of aqueous solution of zinc 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: 21.00
Propylene Glycol: 28.00
Petroleum Jelly: 15.00
Glycerol Monosterate and Polyoxyethylene stearate: 1.00
Zinc Oxide: 2.00
Zinc Gluconate: 2.00
Microcrystalline Wax: 5.00
Water: 26.00
EXAMPLES 4-24
The following are additional specific examples of formulations used to produce cross-linked casts of this invention:
EX. 4
Eastman AQ 55 polymer: 21
Propylene glycol: 28
Zinc gluconate: 2
Water: 49
EX. 5
Eastman AQ 55S polymer: 25.5
Propylene glycol: 34.0
Zinc gluconate: 2.0
Water: 38.5
EX. 6
Eastman AQ 55S polymer: 20.3
Propylene glycol: 18.0
Zinc gluconate: 2.0
Water: 59.7
EX. 7
Eastman AQ 55 S polymer: 23.2
Propylene glycol: 10.0
Zinc gluconate: 2.0
Water: 64.8
EX. 8
Eastman AQ 55S polymer: 21
Propylene glycol: 28
Zinc gluconate: 2
Water: 49
EX. 9
Eastman AQ 55S polymer: 24
Propylene glycol: 32
Zinc gluconate: 2
Water: 42
EX. 10
Eastman AQ 55S polymer: 27
Propylene glycol: 36
Zinc gluconate: 2
Water: 35
EX. 11
Eastman AQ 55S polymer: 23.2
Zinc gluconate: 2.0
Water: 74.8
EX. 12
Eastman AQ 55S polymer: 23.2
Magnesium chloride: 0.5
Water: 76.3
EX. 13
Eastman AQ 55 S polymer: 24
Glycerine: 32
Zinc gluconate: 2
Water: 42
EX. 14
Eastman AQ 55 S polymer: 24.0
Propylene glycol: 32.0
Magnesium chloride: 0.3
Water: 43.7
EX. 15
Eastman AQ 29S polymer: 15.0
Eastman AQ 55S polymer: 5.4
Propylene glycol: 27.2
Mineral oil: 10.0
Polysorbate: 2.0
Zinc gluconate: 3.0
Water: 37.4
EX. 16
Eastman AQ 55S polymer: 20.3
Propylene glycol: 28.0
Mineral oil: 10.0
Petroleum jelly: 7.0
Polysorbate 20: 1.0
Zinc gluconate: 2.0
Water: 31.7
EX. 17
Eastman AQ 55S polymer: 20.3
Propylene glycol: 28.0
Mineral oil: 10.0
Petroleum jelly: 7.0
Polysorbate 20: 1.0
Zinc gluconate: 1.5
Water: 32.2
EX. 18
Eastman AQ 55S polymer: 18.0
Propylene glycol: 24.0
Petroleum jelly: 17.0
Polysorbate 20: 1.0
Zinc gluconate: 2.0
Water: 38.0
EX. 19
Eastman AQ 55S polymer: 21
Propylene glycol: 28
Dimethicone: 19
Petroleum jelly: 9
Glycerolmonostearate and Polyoxyethylene Stearate: 1
Zinc gluconate: 2
Water: 30
EX. 20
Eastman AQ 55S polymer: 21.0
Propylene glycol: 28.0
Petroleum jelly: 17.0
Zinc gluconate: 2.0
Water: 32.0
EX. 21
Eastman AQ 55S polymer: 21.0
Propylene glycol: 28.0
Petroleum jelly: 16.0
Salicylic acid: 2.0
Zinc gluconate: 2.0
Water: .[.10.1.]. .Badd.31.0 .Baddend.
EX. 22
Eastman AQ 55 S polymer: 20.7
Propylene glycol: 27.6
Petroleum jelly: 15.0
Benzoyl peroxide: 2.0
Glycerine: 2.0
Zinc gluconate 2.0
Water: 30.7
EX. 23
Eastman AQ 55 S polymer: 21.0
Propylene glycol: 28.0
Menthol: 2.0
Zinc gluconate: 2.0
Water: .[.26.0.]. .Iadd.47.0 .Iaddend.
Ex. 24
Eastman AQ 55S polymer: 21.0
Propylene glycol: 28.0
Petroleum jelly: 15.0
Polysorbate 20: 1.0
Superabsorbant polymer: 1.0
Zinc gluconate: 1.0
Water: 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.

Claims (3)

What is claimed is:
1. A cross-linked emulsion comprising:
a water dissipatable polymer in an amount from 18 to b 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 composition:
emollient oils in an .[.mount.]. .Iadd.amount .Iaddend.from 0.1 to 25 percent by weight based on the total weight of the composition;
a source of multivalent metallic ions in an .[.mount.]. .Iadd.amount .Iaddend.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.
2. A cross-linked emulsion 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 from the composition of claim 1.
US08/016,808 1989-06-16 1993-02-11 Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom Expired - Lifetime USRE34716E (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US08/016,808 USRE34716E (en) 1989-06-16 1993-02-11 Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/367,183 US4992508A (en) 1989-06-16 1989-06-16 Aqueous dispersions of polyester and polyesteramides cross-linked with metallic ions and casts made therefrom
US57801890A 1990-09-05 1990-09-05
US07/652,233 US5110862A (en) 1989-06-16 1991-02-05 Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom
US08/016,808 USRE34716E (en) 1989-06-16 1993-02-11 Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
US57801890A Continuation 1989-06-16 1990-09-05
US07/652,233 Reissue US5110862A (en) 1989-06-16 1991-02-05 Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom

Publications (1)

Publication Number Publication Date
USRE34716E true USRE34716E (en) 1994-09-06

Family

ID=23446235

Family Applications (3)

Application Number Title Priority Date Filing Date
US07/367,183 Expired - Lifetime US4992508A (en) 1989-06-16 1989-06-16 Aqueous dispersions of polyester and polyesteramides cross-linked with metallic ions and casts made therefrom
US08/016,806 Expired - Lifetime USRE34682E (en) 1989-06-16 1993-02-11 Aqueous dispersions of polyester and polyesteramides cross-linked with metallic ions and casts made therefrom
US08/016,808 Expired - Lifetime USRE34716E (en) 1989-06-16 1993-02-11 Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom

Family Applications Before (2)

Application Number Title Priority Date Filing Date
US07/367,183 Expired - Lifetime US4992508A (en) 1989-06-16 1989-06-16 Aqueous dispersions of polyester and polyesteramides cross-linked with metallic ions and casts made therefrom
US08/016,806 Expired - Lifetime USRE34682E (en) 1989-06-16 1993-02-11 Aqueous dispersions of polyester and polyesteramides cross-linked with metallic ions and casts made therefrom

Country Status (6)

Country Link
US (3) US4992508A (en)
EP (1) EP0413418B1 (en)
AT (1) ATE142663T1 (en)
CA (1) CA2019117C (en)
DE (1) DE69028463T2 (en)
ES (1) ES2091797T3 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5948400A (en) 1997-11-20 1999-09-07 Smith & Nephew Inc. Method of applying a pressure-sensitive adhesive wound dressing and water-based skin treatment composition

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5221254A (en) * 1991-04-02 1993-06-22 Alza Corporation Method for reducing sensation in iontophoretic drug delivery
US5386003A (en) * 1993-03-15 1995-01-31 Eastman Chemical Company Oil absorbing polymers
FR2765480B1 (en) * 1997-07-07 1999-09-10 Oreal USE FOR THE COATING OF KERATIN MATERIALS WITH A HYBRID POLYMERIC MATERIAL; COSMETIC OR DERMATOLOGICAL COMPOSITIONS
US5922782A (en) * 1997-07-23 1999-07-13 Eastman Chemical Company Foamable copolyesters prepared from divalent metal containing co-ionomers
US6274167B1 (en) * 2000-09-14 2001-08-14 Vincent Margiotta Topical anesthetic patch
US20030143264A1 (en) * 2002-01-30 2003-07-31 Vincent Margiotta Topical anesthetic-antiseptic patch
FR2850021A1 (en) * 2003-01-20 2004-07-23 Oreal Foaming aqueous composition, e.g. useful for cleansing or removing make-up from the skin, scalp or hair, comprises an aromatic polyester sulfonate, a foaming nonionic surfactant and a polyvalent cation
US6960748B2 (en) 2003-10-09 2005-11-01 Smurfit-Stone Container Enterprises, Inc. Collapsible microwave popcorn box
CN1893931B (en) * 2003-10-27 2011-07-20 陶氏康宁公司 Preparations for topical application and methods of delivering an active agent to a substrate
US20060084737A1 (en) * 2004-10-15 2006-04-20 Certainteed Corporation Polyester resin binder
US20070259029A1 (en) * 2006-05-08 2007-11-08 Mcentire Edward Enns Water-dispersible patch containing an active agent for dermal delivery
US20070258935A1 (en) * 2006-05-08 2007-11-08 Mcentire Edward Enns Water dispersible films for delivery of active agents to the epidermis
US20080057090A1 (en) * 2006-09-01 2008-03-06 Mcentire Edward Enns Wrinkle masking film composition for skin
US7879942B2 (en) * 2006-10-05 2011-02-01 Eastman Chemical Company Switchable adhesive article for attachment to skin and method of using the same
WO2016130881A1 (en) * 2015-02-12 2016-08-18 Eastman Chemical Company Elastomeric compositions comprising ionomers

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1545403A (en) * 1966-11-28 1968-11-08 Polymer Corp Vulcanizates of diolefin polymers
US3493350A (en) * 1963-07-25 1970-02-03 Phillips Petroleum Co Carbon black feeding to a pelletizer using gas pulses in the flow control zone
US3562034A (en) * 1966-11-28 1971-02-09 Polymer Corp Vulcanization of allylic halide terminated polymers of diolefinic hydrocarbons
US3734874A (en) * 1970-02-27 1973-05-22 Eastman Kodak Co Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt
FR2211474A1 (en) * 1972-12-26 1974-07-19 Exxon Research Engineering Co
US3879168A (en) * 1971-11-29 1975-04-22 Medical Alginates Limited Manufacture of alginic material
US3949742A (en) * 1974-09-20 1976-04-13 Frigitronics, Inc. Medical dressing
US4022880A (en) * 1973-09-26 1977-05-10 Lever Brothers Company Anticalculus composition
US4100269A (en) * 1973-06-28 1978-07-11 Lever Brothers Company Anticalculus dentifrice
US4233196A (en) * 1979-04-30 1980-11-11 Eastman Kodak Company Polyester and polyesteramide compositions
EP0022624A1 (en) * 1979-06-21 1981-01-21 The British Petroleum Company p.l.c. Process for setting a polychloroprene-latex
US4252885A (en) * 1977-03-25 1981-02-24 Bexford Limited Polyester coated films using an aqueous polyester dispersion and photographic layer
US4300580A (en) * 1977-01-07 1981-11-17 Eastman Kodak Company Hair grooming method using linear polyesters
US4304901A (en) * 1980-04-28 1981-12-08 Eastman Kodak Company Water dissipatable polyesters
US4304900A (en) * 1980-04-28 1981-12-08 Eastman Kodak Company Water dissipatable polyesters
US4335220A (en) * 1981-04-06 1982-06-15 Eastman Kodak Company Sequestering agents and compositions produced therefrom
US4393048A (en) * 1980-02-15 1983-07-12 The United States Of America As Represented By The Secretary Of The Army Protective gel composition for wounds
US4409285A (en) * 1980-11-10 1983-10-11 Imperial Chemical Industries Plc Surface-modifying coating compositions
US4478907A (en) * 1981-11-02 1984-10-23 Agfa-Gevaert N.V. Aqueous copolyester dispersions suited for the subbing of polyester film
US4502976A (en) * 1982-10-25 1985-03-05 Bend Research, Inc. Water soluble polyesters
US4704325A (en) * 1984-11-26 1987-11-03 Imperial Chemical Industries Plc Polymeric films
US4724240A (en) * 1981-03-23 1988-02-09 Wickhen Products, Inc. Lattice-entrapped emollient-moisturizer composition
US4787984A (en) * 1987-06-08 1988-11-29 The Drackett Company Cleaning composition and its method of use
US4849213A (en) * 1983-03-01 1989-07-18 Schaeffer Hans A Dental preparation, article and method for storage and delivery therof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3493550A (en) * 1967-07-03 1970-02-03 American Cyanamid Co Plasticized associated polymers
CA1168157A (en) * 1981-03-23 1984-05-29 Eric S. Abrutyn Polymer entrapped emollient-moisturizer composition

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3493350A (en) * 1963-07-25 1970-02-03 Phillips Petroleum Co Carbon black feeding to a pelletizer using gas pulses in the flow control zone
FR1545403A (en) * 1966-11-28 1968-11-08 Polymer Corp Vulcanizates of diolefin polymers
US3562034A (en) * 1966-11-28 1971-02-09 Polymer Corp Vulcanization of allylic halide terminated polymers of diolefinic hydrocarbons
US3734874A (en) * 1970-02-27 1973-05-22 Eastman Kodak Co Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt
US3879168A (en) * 1971-11-29 1975-04-22 Medical Alginates Limited Manufacture of alginic material
FR2211474A1 (en) * 1972-12-26 1974-07-19 Exxon Research Engineering Co
US3887756A (en) * 1972-12-26 1975-06-03 Exxon Research Engineering Co Polymer-base painted resin cured unsaturated elastomeric substrates
US4100269A (en) * 1973-06-28 1978-07-11 Lever Brothers Company Anticalculus dentifrice
US4022880A (en) * 1973-09-26 1977-05-10 Lever Brothers Company Anticalculus composition
US3949742A (en) * 1974-09-20 1976-04-13 Frigitronics, Inc. Medical dressing
US4300580A (en) * 1977-01-07 1981-11-17 Eastman Kodak Company Hair grooming method using linear polyesters
US4252885A (en) * 1977-03-25 1981-02-24 Bexford Limited Polyester coated films using an aqueous polyester dispersion and photographic layer
US4233196A (en) * 1979-04-30 1980-11-11 Eastman Kodak Company Polyester and polyesteramide compositions
EP0022624A1 (en) * 1979-06-21 1981-01-21 The British Petroleum Company p.l.c. Process for setting a polychloroprene-latex
US4393048A (en) * 1980-02-15 1983-07-12 The United States Of America As Represented By The Secretary Of The Army Protective gel composition for wounds
US4304901A (en) * 1980-04-28 1981-12-08 Eastman Kodak Company Water dissipatable polyesters
US4304900A (en) * 1980-04-28 1981-12-08 Eastman Kodak Company Water dissipatable polyesters
US4409285A (en) * 1980-11-10 1983-10-11 Imperial Chemical Industries Plc Surface-modifying coating compositions
US4724240A (en) * 1981-03-23 1988-02-09 Wickhen Products, Inc. Lattice-entrapped emollient-moisturizer composition
US4335220A (en) * 1981-04-06 1982-06-15 Eastman Kodak Company Sequestering agents and compositions produced therefrom
US4478907A (en) * 1981-11-02 1984-10-23 Agfa-Gevaert N.V. Aqueous copolyester dispersions suited for the subbing of polyester film
US4502976A (en) * 1982-10-25 1985-03-05 Bend Research, Inc. Water soluble polyesters
US4849213A (en) * 1983-03-01 1989-07-18 Schaeffer Hans A Dental preparation, article and method for storage and delivery therof
US4704325A (en) * 1984-11-26 1987-11-03 Imperial Chemical Industries Plc Polymeric films
US4787984A (en) * 1987-06-08 1988-11-29 The Drackett Company Cleaning composition and its method of use

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Eastman AQ™ Polymer-A Unique Dispersant For Hydrophobic Materials" by Michael J. Idacavage dated Dec. 1987.
Eastman AQ Polymer A Unique Dispersant For Hydrophobic Materials by Michael J. Idacavage dated Dec. 1987. *
Eastman Publication No. J 257A dated May 1986 entitled Preparation of Water Resistant Coatings and Durable Binders Containing Eastman (WD3652) Water Dispersible Polymers . *
Eastman Publication No. J-257A dated May 1986 entitled "Preparation of Water-Resistant Coatings and Durable Binders Containing Eastman™ (WD3652) Water Dispersible Polymers".

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5948400A (en) 1997-11-20 1999-09-07 Smith & Nephew Inc. Method of applying a pressure-sensitive adhesive wound dressing and water-based skin treatment composition

Also Published As

Publication number Publication date
EP0413418B1 (en) 1996-09-11
DE69028463T2 (en) 1997-02-06
EP0413418A3 (en) 1991-11-27
EP0413418A2 (en) 1991-02-20
ES2091797T3 (en) 1996-11-16
US4992508A (en) 1991-02-12
DE69028463D1 (en) 1996-10-17
CA2019117A1 (en) 1990-12-16
CA2019117C (en) 1999-04-06
USRE34682E (en) 1994-08-02
ATE142663T1 (en) 1996-09-15

Similar Documents

Publication Publication Date Title
USRE34716E (en) Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom
US4950475A (en) Novel film-forming gels with high concentrations of humectants and emollients
DE60108258T2 (en) SELF-ADHESIVE, HYDRATABLE MATRIX FOR THERAPEUTIC APPLICATIONS
US5456745A (en) Flexible, hydrophilic gel film, the process for its production and the use of it
DE69830166T2 (en) NEW MEDICAMENT BASED ON POLYMERS OF METHACRYLAMIDE-MODIFIED GELATINE
US4920158A (en) Hydrogel-forming wound dressing or skin coating material
US4272518A (en) Plastic wound bandage
US5013769A (en) Method of making a hydrogel-forming wound dressing or skin coating material
CA1295796C (en) Biodegradable matrix and methods for producing same
US6461628B1 (en) Non-woven keratin cell scaffold
US5000955A (en) Thermally reversible polyurethane hydrogels and cosmetic, biological and medical uses
AU716244B2 (en) Sterilisable paste product for topical application
US4303066A (en) Burn dressing
US6106855A (en) Protein stabilized oil-in-water emulsions
US5549914A (en) Heat stable wound care gel
ES543595A0 (en) PROCEDURE FOR PREPARING BIOLOGICALLY ACTIVE COMPOSITIONS BASED ON BIOCIDES IN OTHER INGREDIENTS, HYDROPHILIC POLYMERS AND INORGANIC SALTS.
JP2001048737A (en) Solid composition and its use, especially cosmetic use
US2624690A (en) Adhesive compositions comprising polymerized methyl methacrylate, an ester of salicylic acid and an organic solvent
KR20180058641A (en) A Hydrogel Composition Excellent In Moisture Resistance And A Sheet Using The Composition
CZ291190B6 (en) Collagen composition for controlled release of active substances, process of its preparation and use
US4778786A (en) Composition for transdermal drug delivery
GB2049424A (en) Dressing
US2616418A (en) Thermoplastic cast material
CN110038157B (en) Jet type photocuring hydrogel dressing precursor liquid based on polyurethane and preparation method thereof
JPH0368369A (en) Liquid polymer bandage for dermic injury treat- ment

Legal Events

Date Code Title Description
FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: PEOPLE'S BANK, CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:IMAGINATIVE RESEARCH ASSOCIATES, INC.;REEL/FRAME:008478/0808

Effective date: 19970418

Owner name: IMAGINATIVE RESEARCH ASSOCIATES, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CONNECTICUT DEVELOPMENT AUTHORITY;REEL/FRAME:008478/0816

Effective date: 19970425

FPAY Fee payment

Year of fee payment: 8