CA2019117C - Aqueous dispersions of polyester and polyesteramides cross-linked with metallic ions and casts made therefrom - Google Patents
Aqueous dispersions of polyester and polyesteramides cross-linked with metallic ions and casts made therefromInfo
- Publication number
- CA2019117C CA2019117C CA002019117A CA2019117A CA2019117C CA 2019117 C CA2019117 C CA 2019117C CA 002019117 A CA002019117 A CA 002019117A CA 2019117 A CA2019117 A CA 2019117A CA 2019117 C CA2019117 C CA 2019117C
- Authority
- CA
- Canada
- Prior art keywords
- composition
- amount
- percent
- total weight
- weight based
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0212—Face masks
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/85—Polyesters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
- A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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 30 to 80 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 30 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 an amount from 0.1 to 5 percent by weight based on the total weight of the composition;
humectant 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.
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 30 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 an amount from 0.1 to 5 percent by weight based on the total weight of the composition;
humectant 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.
Description
'~ ' 2019117 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.
Many compositions used for skin treatment contain emollients or 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.
Patent 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.
Patent 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.
Patent 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. Patent 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 _ 2019117 content of 2-6% by weight comprised of a laminate of a thin layer of non-porous segmented polyurethane sewn to foam.
U.S. Patent 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 andJor emolIients 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:
HO - G - A - G - A - G - A - G - A - G - ~ - G - A - G - OH
~03~Na S03~Na wherein "A" is an aromatic dicarboxylic acid moiety some of which have sodiofulfo (-SO3- , Na ) sub-stituents, "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 multi-valent 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 compatible with the polymers used in this 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.
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 30 to 80%, humectants in an amount from 0.01 to 7 ~i ' ~,, 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 30-80% 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 composi-tion 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 30-80% by weight based on the total weight of the composition; (c) 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 an amount from 30 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 multi-valent metallic ions in an amount from 0.1 to 5% by weight based on the total weight of the composition;
-,j ~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. Patent No.
3,734,874 to Kibler, et al., U.S. Patent No.
4,233,196 to Sublet and U.S. Patent 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 3~ used in the cosmetic and dermatological fields.
~ ~ 7 ~
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, salicylic 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 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 inflammed 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 I
A clear cross-linked cast was produced having the following composition:
Eastman AQ 55S polymer 24.0 Zinc Gluconate (USP) 2.0 Propylene Glycol 34.0 Water 40.0 . - ' .1_ 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 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 .
20191~7 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 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.
Eastman AQ 55S polymer 21.00 Propylene Glycol28.00 Petroleum Jelly 15.00 Glycerol Monostearate and Polyoxyethylene stearate 1.00 Zinc Oxide 2.00 zinc Gluconate 2.00 Microcrystalline Wax5.00 Water 26.00 The following are additional specific examples of formulations used to produce cross-linked casts of this invention:
~ 2019117 Ex. 4 Eastman AQ 55S polymer 21 Propylene glycol 28 S 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 55S 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 polymer27 Propylene glycol 36 Zinc gluconate 2 Water 35 Ex. 11 Eastman AQ 55S polymer23.2 Zinc gluconate 2.0 Water 74.8 Ex. 12 Eastman AQ 55S polymer23.2 Magnesium chloride 0.5 Water 76.3 Ex. 13 Eastman AQ 55S polymer24 Glycerine 32 Zinc gluconate 2 Water 42 .~,~
Ex. 14 Eastman AQ 55S polymer24.0 Propylene glycol 32.0 Magnesium chloride 0.3 Water 43.7 Ex. 15 Eastman AQ 29S polymer15.0 Eastman AQ 55S polymer5.4 Propylene glycol 27.2 Mineral oil 10.0 Polysorbate 20 2.0 Zinc gluconate 3.0 Water 37.4 Ex. 16 Eastman AQ 55S polymer20.3 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 polymer20.3 Propylene glycol 28.0 Mineral oil 10.0 Petroleum jelly 7.0 Polysorbate 20 1.0 Zinc gluconate 1.5 Water 32.2 C~ ~ ~ 7 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 9 Petroleum jelly 9 Glycerolmonostearate and Polyoxyethylene Stearate 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 31.0 Ex. 22 Eastman AQ 55S 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 55S polymer 21.0 Propylene glycol 28.0 Menthol 2.0 Zinc gluconate 2.0 Water 47.0 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 embodi-ments 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.
Many compositions used for skin treatment contain emollients or 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.
Patent 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.
Patent 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.
Patent 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. Patent 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 _ 2019117 content of 2-6% by weight comprised of a laminate of a thin layer of non-porous segmented polyurethane sewn to foam.
U.S. Patent 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 andJor emolIients 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:
HO - G - A - G - A - G - A - G - A - G - ~ - G - A - G - OH
~03~Na S03~Na wherein "A" is an aromatic dicarboxylic acid moiety some of which have sodiofulfo (-SO3- , Na ) sub-stituents, "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 multi-valent 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 compatible with the polymers used in this 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.
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 30 to 80%, humectants in an amount from 0.01 to 7 ~i ' ~,, 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 30-80% 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 composi-tion 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 30-80% by weight based on the total weight of the composition; (c) 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 an amount from 30 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 multi-valent metallic ions in an amount from 0.1 to 5% by weight based on the total weight of the composition;
-,j ~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. Patent No.
3,734,874 to Kibler, et al., U.S. Patent No.
4,233,196 to Sublet and U.S. Patent 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 3~ used in the cosmetic and dermatological fields.
~ ~ 7 ~
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, salicylic 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 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 inflammed 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 I
A clear cross-linked cast was produced having the following composition:
Eastman AQ 55S polymer 24.0 Zinc Gluconate (USP) 2.0 Propylene Glycol 34.0 Water 40.0 . - ' .1_ 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 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 .
20191~7 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 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.
Eastman AQ 55S polymer 21.00 Propylene Glycol28.00 Petroleum Jelly 15.00 Glycerol Monostearate and Polyoxyethylene stearate 1.00 Zinc Oxide 2.00 zinc Gluconate 2.00 Microcrystalline Wax5.00 Water 26.00 The following are additional specific examples of formulations used to produce cross-linked casts of this invention:
~ 2019117 Ex. 4 Eastman AQ 55S polymer 21 Propylene glycol 28 S 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 55S 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 polymer27 Propylene glycol 36 Zinc gluconate 2 Water 35 Ex. 11 Eastman AQ 55S polymer23.2 Zinc gluconate 2.0 Water 74.8 Ex. 12 Eastman AQ 55S polymer23.2 Magnesium chloride 0.5 Water 76.3 Ex. 13 Eastman AQ 55S polymer24 Glycerine 32 Zinc gluconate 2 Water 42 .~,~
Ex. 14 Eastman AQ 55S polymer24.0 Propylene glycol 32.0 Magnesium chloride 0.3 Water 43.7 Ex. 15 Eastman AQ 29S polymer15.0 Eastman AQ 55S polymer5.4 Propylene glycol 27.2 Mineral oil 10.0 Polysorbate 20 2.0 Zinc gluconate 3.0 Water 37.4 Ex. 16 Eastman AQ 55S polymer20.3 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 polymer20.3 Propylene glycol 28.0 Mineral oil 10.0 Petroleum jelly 7.0 Polysorbate 20 1.0 Zinc gluconate 1.5 Water 32.2 C~ ~ ~ 7 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 9 Petroleum jelly 9 Glycerolmonostearate and Polyoxyethylene Stearate 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 31.0 Ex. 22 Eastman AQ 55S 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 55S polymer 21.0 Propylene glycol 28.0 Menthol 2.0 Zinc gluconate 2.0 Water 47.0 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 embodi-ments 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 (8)
1. A cross-linked aqueous dispersion 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 30 to 80 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.
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 30 to 80 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.
2. A cross-linked dispersion 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.
4. A cross-linked emulsion 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 30 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 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.
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 30 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 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.
5. A cross-linked emulsion according to claim 4 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.
6. An article manufactured from the composition of claim 4.
7. A method of producing a cross-linked cast, the method comprising:
a) forming an aqueous dispersion 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 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 b) pouring said dispersion into a mold whereby there is obtained a cross-linked cast.
a) forming an aqueous dispersion 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 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 b) pouring said dispersion into a mold whereby there is obtained a cross-linked cast.
8. A method of producing a cross-linked cast, the method comprising:
a) forming an emulsion 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 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 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;
emulsifier in an amount of up to 5 percent by weight based on the total weight of the composition;
and b) pouring said emulsion into a mold whereby there is obtained a cross-linked cast.
a) forming an emulsion 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 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 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;
emulsifier in an amount of up to 5 percent by weight based on the total weight of the composition;
and b) pouring said emulsion into a mold whereby there is obtained a cross-linked cast.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US367,183 | 1989-06-16 | ||
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2019117A1 CA2019117A1 (en) | 1990-12-16 |
| CA2019117C true CA2019117C (en) | 1999-04-06 |
Family
ID=23446235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002019117A Expired - Fee Related CA2019117C (en) | 1989-06-16 | 1990-06-15 | 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) |
Families Citing this family (16)
| 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 |
| 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 |
| 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 |
| KR101148013B1 (en) * | 2003-10-27 | 2012-07-05 | 다니스코 유에스 인크. | 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 |
| US20070258935A1 (en) * | 2006-05-08 | 2007-11-08 | Mcentire Edward Enns | Water dispersible films for delivery of active agents to the epidermis |
| US20070259029A1 (en) * | 2006-05-08 | 2007-11-08 | Mcentire Edward Enns | Water-dispersible patch containing an active agent for dermal delivery |
| 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 |
Family Cites Families (26)
| 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 |
| CA849618A (en) * | 1966-11-28 | 1970-08-18 | Polymer Corporation Limited | Vulcanization |
| FR1545403A (en) * | 1966-11-28 | 1968-11-08 | Polymer Corp | Vulcanizates of diolefin polymers |
| US3493550A (en) * | 1967-07-03 | 1970-02-03 | American Cyanamid Co | Plasticized associated polymers |
| 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 |
| 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 |
| GB1589926A (en) * | 1977-03-25 | 1981-05-20 | Bexford Ltd | Coated films |
| US4233196A (en) * | 1979-04-30 | 1980-11-11 | Eastman Kodak Company | Polyester and polyesteramide compositions |
| WO1980002843A1 (en) * | 1979-06-21 | 1980-12-24 | British Petroleum Co | Process for setting a latex of a film forming material |
| 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 |
| US4304900A (en) * | 1980-04-28 | 1981-12-08 | Eastman Kodak Company | Water dissipatable polyesters |
| US4304901A (en) * | 1980-04-28 | 1981-12-08 | Eastman Kodak Company | Water dissipatable polyesters |
| ATE10945T1 (en) * | 1980-11-10 | 1985-01-15 | Imperial Chemical Industries Plc | SURFACE ACTIVE CLOTHING COMPOSITION. |
| US4724240A (en) * | 1981-03-23 | 1988-02-09 | Wickhen Products, Inc. | Lattice-entrapped emollient-moisturizer composition |
| CA1168157A (en) * | 1981-03-23 | 1984-05-29 | Eric S. Abrutyn | Polymer entrapped emollient-moisturizer composition |
| US4335220A (en) * | 1981-04-06 | 1982-06-15 | Eastman Kodak Company | Sequestering agents and compositions produced therefrom |
| DE3273216D1 (en) * | 1981-11-02 | 1986-10-16 | Agfa Gevaert Nv | 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 |
| GB8429772D0 (en) * | 1984-11-26 | 1985-01-03 | Ici Plc | Polymeric films |
| US4787984A (en) * | 1987-06-08 | 1988-11-29 | The Drackett Company | Cleaning composition and its method of use |
-
1989
- 1989-06-16 US US07/367,183 patent/US4992508A/en not_active Expired - Lifetime
-
1990
- 1990-06-14 DE DE69028463T patent/DE69028463T2/en not_active Expired - Fee Related
- 1990-06-14 ES ES90306515T patent/ES2091797T3/en not_active Expired - Lifetime
- 1990-06-14 EP EP90306515A patent/EP0413418B1/en not_active Expired - Lifetime
- 1990-06-14 AT AT90306515T patent/ATE142663T1/en not_active IP Right Cessation
- 1990-06-15 CA CA002019117A patent/CA2019117C/en not_active Expired - Fee Related
-
1993
- 1993-02-11 US US08/016,806 patent/USRE34682E/en not_active Expired - Lifetime
- 1993-02-11 US US08/016,808 patent/USRE34716E/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ES2091797T3 (en) | 1996-11-16 |
| USRE34682E (en) | 1994-08-02 |
| CA2019117A1 (en) | 1990-12-16 |
| DE69028463T2 (en) | 1997-02-06 |
| EP0413418B1 (en) | 1996-09-11 |
| EP0413418A2 (en) | 1991-02-20 |
| USRE34716E (en) | 1994-09-06 |
| EP0413418A3 (en) | 1991-11-27 |
| US4992508A (en) | 1991-02-12 |
| DE69028463D1 (en) | 1996-10-17 |
| ATE142663T1 (en) | 1996-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2019117C (en) | Aqueous dispersions of polyester and polyesteramides cross-linked with metallic ions and casts made therefrom | |
| US4950475A (en) | Novel film-forming gels with high concentrations of humectants and emollients | |
| US4920158A (en) | Hydrogel-forming wound dressing or skin coating material | |
| US5456745A (en) | Flexible, hydrophilic gel film, the process for its production and the use of it | |
| US4591501A (en) | Cosmetic and pharmaceutical sheet material containing polypeptides | |
| DE60108258T2 (en) | SELF-ADHESIVE, HYDRATABLE MATRIX FOR THERAPEUTIC APPLICATIONS | |
| US5013769A (en) | Method of making a hydrogel-forming wound dressing or skin coating material | |
| DE69830166T2 (en) | NEW MEDICAMENT BASED ON POLYMERS OF METHACRYLAMIDE-MODIFIED GELATINE | |
| US2155658A (en) | Surgical and medical preparations | |
| US4671955A (en) | Waterproof sunscreen compositions | |
| AU716244B2 (en) | Sterilisable paste product for topical application | |
| US4291025A (en) | Agar gel topical dressing | |
| DE2135995A1 (en) | Orthopedic casting material | |
| 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 | |
| GB2049424A (en) | Dressing | |
| US2616418A (en) | Thermoplastic cast material | |
| JPH0368369A (en) | Liquid polymer bandage for dermic injury treat- ment | |
| US5110862A (en) | Aqueous dispersions of polyester and polyester-amides cross-linked with metallic ions and casts made therefrom | |
| US4709712A (en) | Polycarboxylic acid polymer gels as protective agents | |
| ITMI20080636A1 (en) | PATCH FOR DERMAL USE | |
| US4186190A (en) | Method of treating burns using a poly-ε-caprolactone | |
| JPH09507833A (en) | Antiperspirant and method of applying antiperspirant using shaped article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |