Polyurethane pressure-sensitive adhesives

• US 5,591,820 A
• Filed: 05/09/1995
• Issued: 01/07/1997
• Est. Priority Date: 11/09/1992
• Status: Expired due to Fees

• Current Assignee: E R Squibb & Sons Incorporated
• Original Assignee: E R Squibb & Sons Incorporated
• Inventors: Jamshidi, Khosrow, Bastar, Ladislav, Kydonieus, Agis, Kuo, Sheng-hung, Shah, Kishore, Chang, Tak-lung
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): Cooney, Jr., John M.
• Application Number:
  US08/437,069
• Time in Patent Office: 609 Days
• Field of Search: 528/76, 528/77, 528/85, 528/905, 428/423.1
• US Class Current: 528/76
• CPC Class Codes: A61B 90/00 Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges protective face masks A41D13/11; surgeon's or patient's gowns or dresses A41D13/12; devices for carrying-off, for treatment of, or for carrying-over, body liquids A61M1/00
• CPC Class Codes: A61L 31/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds A61L31/041 takes precedence
• CPC Class Codes: A61L 31/148 Materials at least partially resorbable by the body
• CPC Class Codes: C08G 18/4804 Two or more polyethers of different physical or chemical nature
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 18/76 aromatic
• CPC Class Codes: C08L 75/06 from polyesters
• CPC Class Codes: C08L 83/10 Block- or graft-copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00
• CPC Class Codes: C09J 175/08 from polyethers
• CPC Class Codes: Y10S 528/905 Polymer prepared from isocyanate reactant has adhesive property
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

Pressure-sensitive adhesives which possess absorptivity and/or permeability properties to remove transepidermal water loss and/or other bodily fluids that come into contact with the adhesive, in combination with a fine balance of cohesion and adhesion properties, can be formulated by controlling the crosslinking of a polyurethane polymer having excess hydroxyl functionality, a glass transition temperature of less than about 0° C., a moisture absorption of at least about 20% of its weight and/or a moisture vapor transmission rate of at least about 300 grams/meter² /24 hours measured at 37° C. and a 90% relative humidity gradient. Adhesives of these polymers possess a peel adhesion to human skin of between about 0.3 and 4 newtons/cm width of the polymer or adhesive.

Claims

1. A pressure-sensitive adhesive comprising a polyurethane polymer formed by the reaction of an isocyanate component and a polyol component having a molecular weight between about 1,000 and 10,000, said components being reacted at a molar ratio of isocyanate moieties to hydroxyl moieties of less than one, said polymer being free from any added tackifying and plasticizing agents, said polymer having a glass transition temperature of less than about 0°

C., a moisture absorption at equilibrium of at least 20% of its weight, and a peel adhesion to human skin of between about 0.3 and 4 newtons/cm width of the polymer, wherein said isocyanate and said polyol components each have a functionality of at least two and wherein at least one of said components has a functionality that is greater than 2, and further wherein said polyurethane polymer is crosslinked to a crosslink density α

of between about 10^-4 and 10^-3 wherein α

is defined by the equation ##EQU5## where i=1 to n where n is the number of the reactant components;

X_i =the mole fraction of the i^th component;

F_i =the functionality of the i^th component;

r=the NCO/OH ratio; and

Mw=the molecular weight of the polyol.

2. The pressure-sensitive adhesive of claim 1 wherein the glass transition temperature is less than about -30°

C., the moisture absorption at equilibrium is at least about 100% of its weight, and the peel adhesion is between about 0.5 and 3.5 newtons/cm width of the polymer.

3. The pressure-sensitive adhesive of claim 1 wherein the polyurethane polymer has a moisture vapor transmission rate of at least about 300 grams/meter² /24 hours measured at 37°

C. and a 90% relative humidity gradient, and a peel adhesion to human skin of between about 0.5 and 3.5 newtons/cm width of the polymer.

4. The pressure-sensitive adhesive of claim 3 wherein the glass transition temperature is less than about -30°

C., and the moisture vapor transmission rate is at least about 500 grams/meter² /24.

5. The pressure-sensitive adhesive of claim 1 wherein the isocyanate component is an aliphatic polyisocyanate and the crosslink density is between about 2×

10^-4 and 10^-3.

6. The pressure-sensitive adhesive of claim 1 wherein the isocyanate component is an aromatic polyisocyanate and the crosslink density is between about 4×

10^-4 and 9×

10^-4.

7. The pressure-sensitive adhesive of claim 1 wherein the molar ratio is between about 0.5 and 0.99.

8. The pressure-sensitive adhesive of claim 1 wherein the molar ratio is between about 0.65 and 0.9.

9. The pressure-sensitive adhesive of claim 1 wherein the polyether polyol is a homopolymer or copolymer containing ethylene oxide or propylene oxide groups.

10. The pressure-sensitive adhesive of claim 1 wherein the polyol component comprises a polyether polyol having a molecular weight of between about 1000 and 10,000 and a functionality of greater than 2 and the isocyanate component has a functionality of 2.

11. The pressure-sensitive adhesive of claim 1 wherein the polyol component is a polyether diol or triol containing at least about 30% by weight of ethylene oxide groups.

12. The pressure-sensitive adhesive of claim 1 wherein the polyol component is a hydroxyl terminated prepolymer.

13. The pressure-sensitive adhesive of claim 1 wherein the isocyanate component is an aliphatic or aromatic diisocyanate or a combination thereof, and the polyol component has a functionality of greater than 2.

14. The pressure-sensitive adhesive of claim 1 wherein the isocyanate component is an isocyanate terminated prepolymer.

15. A method for making a pressure-sensitive adhesive for application to skin which comprises:

providing a mixture of an isocyanate component, having a functionality of at least 2, and a polyol component having a molecular weight of between about 1,000 and 10,000 and also having a functionality of at least 2 at a molar ratio of isocyanate moieties to hydroxyl moieties of less than one;

selecting at least one of the components to have a functionality that is greater than two to facilitate crosslinking; and

reacting the isocyanate and polyol components in the presence of a catalyst to form a polyurethane polymer, said polyurethane polymer being free from any added tackifying and plasticizing agents, having a glass transition temperature of less than about 0°

C., having a moisture absorption of at least about 20% of its weight and/or a moisture vapor transmission rate of at least about 300 grams/meter² /24 hours measured at 37°

C. and 90% relative humidity gradient, and having a peel adhesion to human skin of between about 0.3 and 4 newtons/cm width of the polymer wherein said polyurethane polymer is crosslinked to a crosslink density α

of between about 10^-4 and 10^-3 wherein α

is defined by the equation;

##EQU6## where i=1 to n where n is the number of the reactant components;

X_i =the mole fraction of the i^th component;

F_i =the functionality of the i^th component;

r=the NCO/OH ratio; and

Mw=the molecular weight of the polyol. transmission rate of at least about 300 grams/meter² /24 hours measured at 37°

C. and a 90% relative humidity gradient, and a peel adhesion to human skin of between about 0.3 and 4 newtons/cm width of the polymer.

16. The method of claim 15 which further comprises casting the mixture upon a substrate and heating the mixture at a sufficient temperature and for a sufficient time to form a layer of the polymer.

17. The method of claim 16 wherein the mixture is heated to a temperature of between about 100°

and 150°

C. for a time of between about 1 to 25 minutes.

18. The method of claim 15 which further comprises providing a polyether polyol containing at least about 30% by weight of ethylene oxide groups in order to form a polymer having a moisture absorption at equilibrium of at least about 20% of its weight.

19. The method of claim 15 which further comprises forming an isocyanate terminated prepolymer by reaction of a portion of the polyol component with the isocyanate component prior to reaction of the prepolymer with the remaining polyol component.

20. The method of claim 15 which further comprises selecting the polyol component to have a hydroxyl functionality of greater than 2 to obtain the desired crosslink density.

21. The method of claim 15 which further comprises selecting the isocyanate component to have an isocyanate functionality of greater than 2 to obtain the desired crosslink density.

22. The method of claim 15 which further comprises providing the polymer in the form of a layer upon a backing material.

23. The method of claim 22 which further comprises providing the polymer in the form of a layer upon a release layer.