Methods for the preparation of non-stringy adhesive hydrophilic gels

• US 5,354,790 A
• Filed: 08/31/1992
• Issued: 10/11/1994
• Est. Priority Date: 03/30/1989
• Status: Expired due to Term

• Current Assignee: Ludlow Corporation (Mallinckrodt plc)
• Original Assignee: Nepera, Inc.
• Inventors: Murdock, Keith A., Lennon, Linda, Keusch, Preston, Czap, Christine A.
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): DEWITT, LAVONDA R
• Application Number:
  US07/938,909
• Time in Patent Office: 771 Days
• Field of Search: 523/300, 523/105, 523/111
• US Class Current: 523/300
• CPC Class Codes: A61B 2018/00107 Coatings on the energy applicator
• CPC Class Codes: A61B 5/259 using conductive adhesive means, e.g. gels
• CPC Class Codes: A61L 15/58 Adhesives
• CPC Class Codes: A61L 24/001 Use of materials characterised by their function or physical properties
• CPC Class Codes: A61L 24/0031 Hydrogels or hydrocolloids
• CPC Class Codes: C08J 2300/10 Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• CPC Class Codes: C08J 3/28 Treatment by wave energy or particle radiation
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 39/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: C09J 139/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C09J 171/02 Polyalkylene oxides
• CPC Class Codes: H01M 6/22 Immobilising of electrolyte

Abstract

A method is disclosed for the preparation of non-stringy hydrogels that are comprised of a homogeneous uniform mixture of water and at least one water-soluble high molecular weight polymer. Suitable mixtures may be derived from poly(ethylene oxide) and water or poly(vinyl pyrrolidone), a viscosity enhancing hydrophilic polymer and water, and further, may optionally contain an effective amount of a water-soluble electrolyte to provide conductive non-stringy materials. These polymeric mixtures are crosslinked by exposure to radiant energy to provide gel-like solids which are sufficiently tacky and adhesive to adhere to the subjects'"'"' skin and yet are substantially non-stringy and non-aggressive such that contact with such hydrogels imparts less discomfort to the user. In addition, the consumer utilizing the products of this invention would not experience the objectionable sticky, stringy sensation associated with existing adhesive gels.

Claims

1. A method for the preparation of a non-stringy adhesive hydrophilic gel comprising:

(a) forming a liquid film comprising a homogeneous mixture of water and at least one water-soluble polymer present at a concentration of at least about 7 percent by weight of said mixture, said water-soluble polymer having a weight average molecular weight of at least about 200 kD;

(b) exposing said film to a dose of radiant energy within an area of a plot of radiation dose versus polymer concentration whose upper and lower boundaries are defined by the equations NS(C) and A(C), respectively;

Lower Dose, A(C), >

1.245+0.0373C-3.908/C

Upper Dose, NS(C), ≦

2,039+0.1598C-8.183/C

in which C is the concentration of the polymer expressed as a weight fraction of the total mixture, which dose is effective to provide a non-stringy hydrophilic gel which exhibits a sharp, substantially featureless force-displacement profile, has an Adhesion Energy Density (AED) of at least about 5 to less than about 50 g/cm and has a peak-force value of at least about 180 grams.

3. The method of claim 1, or 2 which further comprises adding an amount of a water-soluble electrolyte to said mixture effective to reduce the transverse electrical resistance of said gel to an impedance at 60 Hz of less than about 1,000 ohms.

4. The method of claim 1, or 2 in which said water-soluble polymer is present at a concentration of at least about 7 to less than about 35 percent by weight of said mixture.

5. The method of claim 1, or 2 which further comprises uniformly dispersing an additive in said mixture.

6. The method of claim 5 in which said additive is selected from the group consisting of preservatives, stabilizers, fire retardants, pigments, refractive particles, bactericides, fungicides, antibiotics, cosmetics, moisturizers, pharmaceuticals, therapeutic agents, and mixtures thereof.

7. The method of claim 5 in which said additive is present at a concentration of about 0.001 percent to about 6 percent by weight of said mixture.

8. The method of claim 1 or 2 which further comprises contacting a low area-weight scrim with said gel.

9. The method of claim 8 in which said scrim is manufactured from a synthetic water-insoluble polymer.

10. The method of claim 3 in which said electrolyte is an inorganic salt.

11. The method of claim 3 in which said electrolyte is selected from the group consisting of alkali metal salts, alkaline earth metal salts, and mixtures thereof.

12. The method of claim 3 in which said electrolyte is selected from the group consisting of potassium chloride, sodium chloride, magnesium sulfate, magnesium acetate, and mixtures thereof.

13. The method of claim 3 in which said electrolyte is present at a concentration of about 0.1 weight percent to about 10 weight percent of said mixture.

14. The method of claim 1, or 2 in which said mixture has a viscosity of at least about 8,000 cps.

15. The method of claim 1, or 2 which further comprises adding an amount of a water-soluble electrolyte to said mixture effective to reduce the transverse electrical resistance of said mixture to an impedance at frequencies between about 10 Hz to about 5 MHz of less than about 100 ohms.

16. The method of claim 1 or 2 in which said water-soluble polymer is poly(ethylene oxide).

17. The method of claim 1 or 2 in which said water-soluble polymer comprises poly(vinylpyrrolidone) present at a concentration of about 10 to about 25 percent of said mixture.

18. The method of claim 1 or 2 in which said water-soluble polymer has a weight average molecular weight of at least about 500 kD to about 5,000 kD.

19. The method of claim 1 or 2 further comprising adding a physiologically active agent to said film.

20. The method of claim 1 or 2 which further comprises adding a therapeutic drug to said film.

21. The method of claim 1 or 2 in which further comprises adding a cosmetic formulation to said film.

22. The method of claim 1 or 2 in which further comprises adding at least one preservative to said film.

23. The method of claim 1 or 2, in which said AED value is at least about 7 to less than about 40 g/cm.

24. The method of claim 23 in which said peak-force has a value of at least about 250 grams.

25. The method of claim 23 in which said peak-force has a value of at least about 400 grams.

26. The method of claim 16 in which said poly(ethylene oxide) is present at a concentration of at least about 7 to about 15 percent by weight of said film.

27. The method of claim 17 in which said poly(vinyl pyrrolidone) is present at a concentration of at least 10 to about 25 percent by weight of said film.

28. The method of claim 5 wherein the additive comprises a therapeutic agent.

29. The method of claim 1 or 2 wherein the film is subjected to a dose of radiant energy equivalent to greater than about 0.5 Mrad to less than about 4.5 Mrad.

30. The method of claim 1 or 2 wherein the film is subjected to a dose of radiant energy equivalent to greater than about 0.75 Mrad to less than about 2.5 Mrad.

31. The method of claim 20 wherein the water soluble polymer further comprises a viscosity enhancing hydrophilic polymer having a weight average molecular weight in excess of about 100 kD.

32. The method of claim 3 in which said viscosity enhancing hydrophilic polymer is selected from the group consisting of polyacrylamide, poly(vinyl alcohol), polyacrylate, poly(ethylene oxide), poly(ethylene imine), carboxymethylcellulose, methylcellulose, polyacrylamide sulfonic acid, polyacrylonitrile, agar, dextran, dextrin, carrageenan, xanthan, guar, derivatives, mixtures, blends, and copolymers thereof.

33. The method of claim 17 in which said viscosity enhancing hydrophilic polymer comprises a cellulose derivative.

34. The method of claim 17 in which said viscosity enhancing hydrophilic polymer is present at a concentration of about 0.5 to about 5 percent by weight of said mixture.

2. A method for the preparation of a non-stringy adhesive hydrophilic gel comprising:

(a) forming a liquid film comprising a homogeneous mixture of water and at least one water-soluble polymer present at a concentration of at least about 7 percent by weight of said mixture, said water-soluble polymer having a weight average molecular weight of at least about 200 kD;

(b) exposing said film to a dose of radiant energy within an area of a plot of radiation dose versus polymer concentration whose upper and lower boundaries are defined by the equations NS(C) and A(C), respectively;

Lower Dose, A(C), >

1.245+0.0373C-3.908/C

Upper Dose, NS(C), ≦

2,039+0.1598C-8.183/C

in which C is the concentration of the polymer expressed as a weight fraction of the total mixture, which dose is effective to provide a non-stringy adhesive hydrophilic gel (i) having a gel fraction in the Polymer Extraction Test of at least about 0.8;

(ii) having an Adhesion Energy Density in the Adhesion Energy Density Determination Test of at least about 5 g/cm but not exceeding about 50 gm/cm;

(iii) which gives a rolling ball distance of at least about 10 mm in the Tack Rolling Ball Method in which the ball employed has a diameter of 16.5 mm; and

(iv) has a peak-force value of at least about 180 grams.