Hydrophilic pressure sensitive adhesives

• US 5,489,624 A
• Filed: 12/01/1992
• Issued: 02/06/1996
• Est. Priority Date: 12/01/1992
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Stefely, James S., Kantner, Steven S., Rustad, Nancy J.
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): DEWITT, LAVONDA R
• Application Number:
  US07/983,688
• Time in Patent Office: 1,162 Days
• Field of Search: 523/111, 524/376, 524/377, 524/379, 428/355
• US Class Current: 524/376
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/22 Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
• CPC Class Codes: C09J 171/00 Adhesives based on polyethers obtained by reactions forming an ether link in the main chain based on polyacetals C09J159/00; based on epoxy resins C09J163/00; based on polythioether-ethers C09J181/02; based on polyethersulfones C09J181/06; Adhesives based on derivatives of such polymers
• CPC Class Codes: C09J 171/02 Polyalkylene oxides
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01B 1/20 Conductive material dispersed in non-conductive organic material organic macromolecular compounds or compositions C08
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y10S 428/913 Material designed to be responsive to temperature, light, moisture
• CPC Class Codes: Y10T 428/2839 with release or antistick coating
• CPC Class Codes: Y10T 428/2852 Adhesive compositions
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]

Abstract

A hydrophilic, pressure sensitive adhesive of a poly(ethylene oxide) derived network plasticized with an essentially non-volatile, polar plasticizer present in an amount sufficient to form a cohesive, pressure sensitive adhesive. The polymeric network is prepared from an oligomeric precursor comprising difunctional poly(ethylene glycol) moieties which have been end-capped with ethylenically unsaturation. The adhesive is useful as a biomedical adhesive for transmitting or receiving electrical signals as a component of a biomedical electrode. The adhesive is also useful as a drug delivery device to deliver pharmaceuticals or other active ingredients to or through mammalian skin. The adhesive is also useful as a component in a skin covering for protecting mammalian skin or mammalian skin openings with antimicrobial agents. A method of preparation of the adhesive is also disclosed.

Claims

1. A hydrophilic, pressure sensitive adhesive comprising:

a poly(ethylene oxide) derived network plasticized with an essentially non-volatile, polar plasticizer present in an amount sufficient to form a cohesive, pressure sensitive adhesive, wherein the network is prepared from an oligomeric precursor comprising difunctional poly(ethylene glycol) moieties which have been end-capped with ethylenically unsaturated functionality and wherein the amount of oligomeric precursor in the pressure sensitive adhesive ranges from about 4 to 60 weight percent of the pressure sensitive adhesive.

2. The adhesive according to claim 1, wherein the oligomeric precursor comprises a compound of the formula:

space="preserve" listing-type="equation">X--Y--[(CH.sub.2 CH.sub.2 O).sub.n --R--O--].sub.p --(CH.sub.2 CH.sub.2 O).sub.n --CH.sub.2 CH.sub.2 --Y--X

wherein

X are monovalent moieties having ethylenic unsaturation,

Y are organic divalent linking groups which serve to activate X towards free radical polymerization,

R is an organic divalent linking group,

n is an integer of about 10 to about 350,

and p is an integer of about 0 to about 30, such that 45<

n(p+1)<

450.

3. The adhesive according to claim 2, wherein the network comprises from about 4 to about 60 weight percent of the pressure sensitive adhesive and the essentially non-volatile polar plasticizer is a hydroxy-containing plasticizer comprises from about 96 to about 40 weight percent of the adhesive.

4. The adhesive according to claim 1, wherein the essentially non-volatile plasticizer is selected from the group consisting of monohydric alcohols, polyhydric alcohols, aromatic alcohols, and mixtures of water and such alcohols where the amount of alcohol is sufficient to render the plasticizer essentially non-volatile.

5. The adhesive according to claim 2, wherein the molecular weights for the difunctional poly(ethylene glycol) range from about 2,000 to about 20,000 g/mole.

6. The adhesive according to claim 5, wherein the weight percent of the network ranges from about 15 to about 25 weight percent of the adhesive and the molecular weight for the difunctional poly(ethylene glycol) ranges from about 6,000 to about 12,000 g/mole.

7. The adhesive according to claim 2, wherein the network is prepared by free radical polymerization of the oligomeric precursor using free radicals generated from thermal, redox, or photochemical initiators or due to exposure of the oligomeric precursor to actinic radiation.

8. The adhesive according to claim 2, wherein X comprises R'"'"'CH═

C(R")--, wherein R'"'"' is selected from the group consisting of hydrogen and --COOH and R" is selected from the group consisting of hydrogen, methyl, and --CH₂ COOH.

9. The adhesive according to claim 8, wherein R'"'"' comprises hydrogen and R" is selected from the group consisting of hydrogen and methyl.

10. The adhesive according to claim 2, wherein organic divalent linking group Y is generated upon reaction of an electrophile with an diamine or diol and is chosen so as to activate the ethylenically unsaturated monovalent X group towards free radical polymerization.

11. The adhesive according to claim 10, wherein Y is selected from the group of structures containing aromatic moieties which, when bound to X, yield vinyl pyridinyl or styrenic functionalities;

structures containing carboxyl moieties which when bound to X at the oxygen side yield vinyl ester or isopropenyl ester functionalities;

structures containing carboxyl moieties which when bound to X at the carbonyl side yield acrylate, methacrylate, maleate, fumarate, and itaconate functionalities;

structures containing carboxamide moieties which when bound to X at the nitrogen side yield N-vinyl amide and N-isopropenyl amide functionality; and

structures containing carboxamide moieties which when bound to X at the carbonyl side yield acrylamide, methacrylamide, and maleimide functionalities.

12. The adhesive according to claim 10 wherein the electrophile comprises an acid halide, an acid anhydride, a cyclic anhydride, an azlactone, an isocyanate, benzyl halide, an epoxy or an acrylate.

13. The adhesive according to claim 12, wherein the electrophile comprises isocyanatoethyl methacrylate;

alkenyl azlactones;

m-isopropenyl-alpha, alpha-dimethyl benzyl isocyanate;

glycidyl methacrylate;

acryloyl ethyl carbonic anhydride;

maleic anhydride;

methacrylic anhydride;

hexanediol diacrylate;

or trimethylol propane triacrylate.

14. The adhesive according to claim 10, where the diol is derivatized through an esterification reaction with acrylic acid, or through a transesterification reaction with an alkyl acrylate.

15. The adhesive according to claim 10, wherein the diol or diamine is reacted first with a compound comprising two electrophilic groups and the resultant product then reacted in a second step with a nucleophile comprising an amine or an alcohol to provide the terminally difunctional oligomeric precursor.

16. The adhesive according to claim 15, wherein the nucleophile comprises hydroxyethyl acrylate, hydroxyethyl methacrylate, or hydroxypropyl methacrylate.

17. The adhesive according to claim 1, further comprising an electrolyte for use as an adhesive conductive medium in a biomedical electrode.

18. The adhesive according to claim 1, further comprising an antimicrobial agent for use in adhesively contacting mammalian skin.

19. The adhesive according to claim 1, further comprising pharmaceutical agent for use as an adhesive layer for contacting mammalian skin as a topical, transdermal, or iontophoretic delivery device.