Pressure sensitive conductive adhesive having hot-melt properties and biomedical electrodes using same

• US 6,232,366 B1
• Filed: 06/09/1999
• Issued: 05/15/2001
• Est. Priority Date: 06/09/1999
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Wang, DanLi, Everaerts, Albert I., Stark, Peter A.
• Primary Examiner(s): Kopec, Mark
• Application Number:
  US09/328,334
• Time in Patent Office: 706 Days
• Field of Search: 252/500, 156/327, 156/322, 525/209, 525/221, 523/103, 523/111, 600/391, 424/448, 428/41.5
• US Class Current: 523/111
• CPC Class Codes: A61B 5/259 using conductive adhesive means, e.g. gels
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: C08L 79/02 Polyamines
• CPC Class Codes: C09J 133/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• CPC Class Codes: C09J 2301/302 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
• CPC Class Codes: Y10T 428/1462 Polymer derived from material having at least one acrylic or alkacrylic group or the nitrile or amide derivative thereof [e.g., acrylamide, acrylate ester, etc.]

Abstract

A skin-compatible, hot-melt processible, pressure sensitive adhesive is disclosed. A thermo-reversible cross-linking is achieved, permitting advantages in processibility and the reduction of waste.

Claims

1. A skin-compatible, hot-melt processible, pressure sensitive adhesive, comprising:

between about 30 to 45 parts by weight of a copolymer comprised of between about 30 to 45 parts by weight of an (meth)acrylate ester monomer having C₄-C₂₀ alkyl chains, and between about 55 to 70 parts by weight of an acidic comonomer;

between about 0 to 35 parts by weight of a hydrophilic plasticizer;

between about 20 to 40 parts by weight of water,

between about 0 to 3 parts by weight of a water soluble salt,

between about 10 to 20 parts by weight of a surfactant, and

between about 0.5 to 10 parts by weight of a polymer having amine functionality.

2. The adhesive according to claim 1 wherein the hydrophilic plasticizer is selected from the group consisting of polyethylene oxide, glycerin, and combinations thereof.

3. The adhesive according to claim 1 wherein the adhesive can be melt processed at a temperature between about 50°

C. to 100°

C.

4. The adhesive according to claim 3 wherein the adhesive can be melt processed at a temperature between about 55°

C. to 85°

C.

5. The adhesive of claim 1, wherein the (meth)acrylate monomer has a formula of

wherein R¹ is H or CH₃, the latter corresponding to where the (meth)acrylate monomer is a methacrylate monomer, wherein R² is selected from the group consisting of linear, branched, aromatic, and cyclic hydrocarbon groups.

6. The adhesive of claim 1, wherein the (meth)acrylate monomer is selected from the group consisting of benzyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, decyl acrylate, 2-ethoxy ethyl acrylate, 2-ethoxy ethyl methacrylate, 2-ethylhexyl acrylate, n-hexadecyl acrylate, n-hexadecyl methacrylate, hexyl acrylate, isoamyl acrylate, isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isodecyl acrylate, isodecyl methacrylate, isononyl acrylate, isooctyl acrylate, isooctyl methacrylate, isotridecyl acrylate, lauryl acrylate, lauryl methacrylate, 2-methyl butyl acrylate, 4-methyl-2-pentyl acrylate, 1-methylcyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, 3-methylcyclohexyl methacrylate, 4-methylcyclohexyl methacrylate, octadecyl acrylate, octadecyl methacrylate, n-octyl acrylate, n-octyl methacrylate, 2-phenoxy ethyl methacrylate, n-tetradecyl acrylate, n-tetradecyl methacrylate, and mixtures thereof.

7. The adhesive of claim 1, wherein the (meth)acrylate monomers are selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, and mixtures thereof.

8. The adhesive of claim 1, wherein the acidic comonomer is selected from the group consisting of ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids, and mixtures thereof.

9. The adhesive of claim 1, wherein the surfactant is selected from the group consisting of non(co)polymerizable nonionic surfactants, ethylenically-unsaturated copolymerizable nonionic surfactants, and mixtures thereof.

10. The adhesive of claim 1, wherein the polymer having amine functionality is selected from the group consisting of poly(vinyl amines), poly(allyl amines), poly(alkylene amines), poly(ethylenimine) and alkylated versions thereof, poly(vinyl pyridines), poly(vinyl pyrroles), poly(N-vinyl lactams), and homopolymers or copolymers from monomers of a formula of

wherein

a is 0 or 1;

R is selected from H— and

CH₃—

,

X is selected from —

O— and

—

NH—

;

Y is a divalent linking group selected from the group consisting of groups having about 1 to about 5 carbon atoms and heteroatomic groups having at least one carbon atom and at least one atom of O, S, or N; and

Am is selected from the group consisting of pyridinyl or imidazolyl, and an amine fragment, primary, secondary or tertiary, of a formula;

wherein R¹ and R² are selected from H, alkyl, aryl, cycloalkyl, heterocyclic, and arenyl groups.

11. The adhesive of claim 1, wherein the polymer of amine functionality is poly(ethylenimine).

18. A biomedical electrode, comprising:

a field of adhesive conductive medium according to claim 1 for contacting mammalian skin and a means for electrical communication for interfacing with the adhesive conductive medium and electrical diagnostic, therapeutic, or electrosurgical instrumentation, the adhesive conductive medium adhered to the means for electrical communication.

19. The biomedical electrode according to claim 18, wherein the means for electrical communication comprises a conductor member having an interface portion contacting the adhesive conductive medium and a tab portion available for mechanical and electrical contact with the electrical diagnostic, therapeutic, or electrosurgical instrumentation.

20. A pharmaceutical delivery device comprising:

an adhesive layer for contacting mammalian skin and a backing layer, the adhesive layer adhered to the backing layer and comprising a pressure sensitive adhesive composition according to claim 1.

21. The pharmaceutical delivery device according to claim 20, wherein the adhesive layer further comprises a topical, transdermal, or iontophoretic therapeutic agent or pharmaceutical.

22. The pharmaceutical delivery device according to claim 20, wherein the adhesive layer further comprises an excipient, a solvent, or a penetration enhancing agent.

12. A method for preparing skin-compatible, hot-melt processible, pressure sensitive adhesive, comprising the steps of:

a) preparing a mixture of ethylenically unsaturated monomers comprising;

between about 30 to 45 parts by weight of an (meth)acrylate ester monomer having C₄-C₂₀ alkyl chains, and

between about 55 to 70 parts by weight of an acidic comonomer;

b) mixing between about 30 to 45 parts by weight of the mixture of ethylenically unsaturated monomers with between about 0 to 35 parts by weight of a hydrophilic plasticizer so as to form a hydrophilic plasticizer/monomer mixture;

c) polymerizing the monomers to form a polymer matrix containing the plasticizer;

d) blending an additive mixture into the polymer matrix, the additive mixture comprising

between about 20 to 40 parts by weight of water,

between about 0 to 3 parts of a water soluble salt,

between about 10 to 20 parts by weight of a surfactant, and

between about 0.5 to 10 parts by weight of a polymer having amine functionality, so as to form a skin-compatible hot-melt processible, ionically conductive, pressure sensitive adhesive.

14. The method according to claim 12 further comprising the step of melting the polymer matrix prior to the adding step so that the adding step forms the skin-compatible hot-melt processible, ionically conductive, pressure sensitive adhesive in a molten state.

13. A method for preparing skin-compatible, hot-melt processible, pressure sensitive adhesive, comprising the steps of:

a) preparing a mixture of ethylenically unsaturated monomers comprising;

between about 30 and about 45 parts by weight of an (meth)acrylate ester monomer having C₄-C₁₂ alkyl chains, and

between about 55 and about 70 parts by weight of an acidic comonomer;

b) mixing between about 30 and about 45 parts by weight of the mixture of ethylenically unsaturated monomers with between about 0 and about 35 parts by weight of a hydrophilic plasticizer, between about 10 and about 30 parts by weight of water, between about 0 and about 3 parts by weight of a water soluble salt, and between about 0 and about 7 parts by weight of a surfactant, so as to form a hydrophilic plasticizer/monomer/surfactant/water mixture;

c) polymerizing of the monomers to form a polymer matrix containing plasticizer, water, and surfactant;

d) blending an additive mixture into the polymer matrix, the additive mixture comprising

between about 1 and about 3 parts by weight of a water soluble salt,

between about 10 and about 30 parts by weight of water,

between about 10 and about 13 parts by weight of a surfactant, and

between about 0.5 and about 10 parts by weight of a polymer having amine functionality,

so as to form a skin-compatible hot-melt processible, ionically conductive, pressure sensitive adhesive.

15. The method according to claim 13 further comprising the step of melting the polymer matrix prior to the adding step so that the adding step forms the skin-compatible hot-melt processible, ionically conductive, pressure sensitive adhesive in a molten state.

16. The method according to claim 15 wherein the melting step is performed at a temperature between about 50°

C. to 100°

C.

17. The method according to claim 15 further comprising the step of dispensing the molten adhesive onto a backing.