Water-absorbent adhesive compositions and associated methods of manufacture and use

• US 8,617,647 B2
• Filed: 08/24/2012
• Issued: 12/31/2013
• Est. Priority Date: 05/01/2001
• Status: Expired due to Term

• Current Assignee: Corium LLC
• Original Assignee: AV Topchiev Institute of Petrochemical Synthesis, Corium International, Inc.
• Inventors: Feldstein, Mikhail M., Bairamov, Danir F., Novikov, Mikhail Borisovich, Kulichikhin, Valery G., Plat, Nicolai A., Cleary, Gary W., Singh, Parminder
• Primary Examiner(s): Yoon, Tae H
• Application Number:
  US13/594,746
• Publication Number:
  US 20120321569A1
• Time in Patent Office: 494 Days
• Field of Search: 427/208, 523/111, 524/386, 524/391, 424/49, 424/613, 264/176.1
• US Class Current: 427/208
• CPC Class Codes: A61K 2800/262 Transparent; Translucent
• CPC Class Codes: A61K 2800/54 Polymers characterized by specific structures/properties
• CPC Class Codes: A61K 47/32 Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers , poly(meth)acrylates, or polyvinyl pyrrolidone
• CPC Class Codes: A61K 8/042 Gels
• CPC Class Codes: A61K 8/8152 Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• CPC Class Codes: A61K 8/8176 Homopolymers of N-vinyl-pyrrolidones. Compositions of derivatives of such polymers
• CPC Class Codes: A61K 8/8182 Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
• CPC Class Codes: A61K 8/86 Polyethers
• CPC Class Codes: A61L 15/42 Use of materials characterised by their function or physical properties liquid bandages A61L26/00
• CPC Class Codes: A61L 15/585 Mixtures of macromolecular compounds
• CPC Class Codes: A61P 17/02 for treating wounds, ulcers, burns, scars, keloids, or the like
• CPC Class Codes: A61Q 11/00 Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
• CPC Class Codes: B05D 5/10 to obtain an adhesive surface
• CPC Class Codes: C08K 5/06 Ethers; Acetals; Ketals; Ortho-esters
• CPC Class Codes: C08K 5/11 of acyclic polycarboxylic acids
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 33/04 Homopolymers or copolymers of esters C08L43/04 takes precedence
• 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 133/14 of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen

Abstract

An adhesive composition is provided that is water-insoluble yet water-absorbent, i.e., capable of absorbing up to 15 wt. % water or more. The composition in composed of a film-forming hydrophilic polymer with at least one linear segment having a plurality of recurring polar groups along the polymer backbone, a complementary multifunctional polymer with a plurality of recurring functional groups that noncovalently bind to the polar groups on the film-forming polymer, and plasticizer. A method for manufacturing the adhesive composition is provided as well.

Claims

1. A method for improving the adhesion of a water-insoluble, water-absorbent adhesive composition, by combining, under conditions effective to form a substantially homogeneous admixture:

(a) a film-forming, hydrophilic polymer (FFHP) containing a plurality of recurring polar groups, the FFHP selected from the group consisting of poly(dialkyl aminoalkyl acrylates), poly(dialkylaminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), polyvinyl amine), poly(alkylene imine), poly(N-vinyl acrylamide), poly(N-vinyl alkylacrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), chitosan, copolymers thereof, and combinations of any of the foregoing;

(b) a complementary multifunctional polymer (CMP) that is a polyacid-acrylate polymer bearing recurring carboxyl groups, the CMP selected from the group consisting of copolymers of an alkyl methacrylate and acrylic or methacrylic acid, copolymers of an alkyl acrylate and acrylic or methacrylic acid, and combinations thereof, wherein the CMP has a molecular weight lower than the molecular weight of the FFHP, and the FFHP and the CMP are selected such that the carboxyl groups contained in the CMP are capable of non-covalently binding to the recurring polar groups in the FFHP, and where at least one of the FFHP and the CMP possesses ionogenic groups;

(c) a relatively low molecular weight plasticizer capable of plasticizing the FFHP, the plasticizer selected from the group consisting of polyethylene glycols, polyalcohols, and mixtures thereof;

(d) a solvent in an amount effective to provide a solution,

the improvement comprising;

(i) choosing a weight fraction amount of the FFHP that is greater than the weight fraction amount of the CMP,

(ii) adding to the solution, or to the FFHP or CMP prior to the choosing step, an ionizing agent in an amount effective to ionize up to 30% of the ionogenic groups in the solution or in the FFHP and/or CMP, respectively,

(iii) casting the resulting solution from (d) onto a substrate, and

(iv) heating the solution-coated substrate to volatilize the solvent;

wherein the resulting adhesive composition from (iv) displays an adhesion that is enhanced over the adhesion for the same composition absent the ionizing agent.

19. The method of claim 1, wherein the FFHP is a copolymer of 2-dimethylaminoethyl methacrylate, butyl methacrylate and methyl methacrylate and the CMP is a copolymer of methacrylic acid and methyl methacrylate.

20. The method of claim 1 or claim 2, wherein the ionizing agent is added in an amount effective to ionize from about 5% to about 10% of the ionogenic groups in the solution or in the FFHP and/or CMP respectively.

2. A method for improving the adhesion of a water-insoluble, water-absorbent adhesive composition, by combining, under conditions effective to form a substantially homogeneous admixture:

(a) a film-forming, hydrophilic polymer (FFHP) containing a plurality of recurring polar groups, the FFHP selected from the group consisting of poly(dialkyl aminoalkyl acrylates), poly(dialkylaminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), polyvinyl amine), poly(alkylene imine), poly(N-vinyl acrylamide), poly(N-vinyl alkylacrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), chitosan, copolymers thereof, and combinations of any of the foregoing;

(b) a complementary multifunctional polymer (CMP) that is a polyacid acrylate polymer bearing recurring carboxyl groups, the CMP selected from the group consisting of copolymers of an alkyl methacrylate and acrylic or methacrylic acid, copolymers of an alkyl acrylate and acrylic or methacrylic acid, and combinations thereof, wherein the CMP has a molecular weight lower than the molecular weight of the FFHP, and the FFHP and the CMP are selected such that the carboxyl groups contained in the CMP are capable of non-covalently binding to the recurring polar groups in the FFHP, and where at least one of the FFHP and the CMP possesses ionogenic groups;

(c) a relatively low molecular weight plasticizer capable of plasticizing the FFHP, the plasticizer selected from the group consisting of polyethylene glycols, polyalcohols, and mixtures thereof;

the improvement comprising;

(i) choosing a weight fraction amount of the FFHP that is greater than the weight fraction amount of the CMP,

(ii) adding to the admixture, or to the FFHP or CMP prior to the choosing step, an ionizing agent in an amount effective to up to 30% of the ionogenic groups in the admixture or in the FFHP and/or CMP respectively,

(iii) melt-blending the resulting admixture, and

(iv) extruding;

wherein the resulting adhesive composition displays an adhesion that is enhanced over the adhesion for the same composition absent the ionizing agent.

3. The method of claim 2, wherein the plasticizer is a polyethylene glycol.

4. The method of claim 2, wherein the plasticizer is a polyalcohol.

5. The method of claim 2, wherein the molecular weight of the FFHP is in a range of approximately 20,000 to 3,000,000 Da.

6. The method of claim 5, wherein the molecular weight of the FFHP is in a range of approximately 100,000 to 2,000,000 Da.

7. The method of claim 6, wherein the molecular weight of the FFHP is in a range of approximately 100,000 to 1,500,000 Da.

8. The method of claim 2, wherein the molecular weight of the CMP is in a range of approximately 10,000 to 1,000,000 Da.

9. The method of claim 8, wherein the molecular weight of the CMP is in a range of approximately 100,000 to 1,000,000 Da.

10. The method of claim 2, wherein:

the FFHP is selected from the group consisting of poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), copolymers thereof, and combinations of any of the foregoing; and

the CMP is a copolymer of methacrylic acid and alkyl acrylate.

11. The method of claim 2, wherein

the FFHP is selected from the group consisting of poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), copolymers thereof, and combinations of any of the foregoing;

and

the CMP is a copolymer of methacrylic acid and methyl methacrylate.

12. The method of claim 2, further comprising combining at least one optional additive with the FFHP, the CMP, and the plasticizer during formation of the admixture.

13. The method of claim 12, wherein the at least one additive includes an active agent.

14. The method of claim 13, wherein the at least one additive is a pharmacologically active agent.

15. The method of claim 14, wherein the pharmacologically active agent is a drug.

16. The method of claim 13, wherein the at least one additive is a cosmeceutically active agent.

17. The method of claim 16, wherein the cosmeceutically active agent is a tooth whitening agent.

18. The method of claim 12, wherein the at least one additive is selected from the group consisting of fillers, pH regulating agents, tackifiers, electrolytes, antimicrobial agents, antioxidants, preservatives, colorants, and combinations thereof.