Surgical adhesive

• US 4,994,542 A
• Filed: 03/07/1989
• Issued: 02/19/1991
• Est. Priority Date: 03/07/1988
• Status: Expired due to Term

• Current Assignee: Asahi Glass Company, Limited (AGC, Inc.), Sanyo Chemical Industries Limited
• Original Assignee: Asahi Glass Company, Limited (AGC, Inc.), Sanyo Chemical Industries Limited
• Inventors: Matsuda, Takehisa, Itoh, Tetsuo, Takakura, Teruo
• Primary Examiner(s): WELSH JR, MAURICE
• Application Number:
  US07/320,054
• Time in Patent Office: 714 Days
• Field of Search: 528/70, 528/904
• US Class Current: 528/70
• CPC Class Codes: A61L 24/0073 with a macromolecular matrix
• CPC Class Codes: C08F 283/00 Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/307 Atmospheric humidity
• CPC Class Codes: C08G 18/4833 Polyethers containing oxyethylene units
• CPC Class Codes: C08G 18/4837 and other oxyalkylene units
• CPC Class Codes: C08G 18/6674 with compounds of group C08G18/3203
• CPC Class Codes: C08G 18/773 halogens
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C09J 175/08 from polyethers
• CPC Class Codes: Y10S 528/904 Isocyanate polymer having stated hydrophilic or hydrophobic property

Abstract

Elastomeric or flexible surgical adhesives, comprising (i) a NCO-terminated hydrophilic urethane prepolymer derived from a fluorine-containing polyisocyanate and a hydrophilic polyether polyol of higher oxyethylene content, or a combinatioin of (i) with (ii) an unsaturated cyano compound containing a cyano group directly bonded to a polymerizable double bond, exhibit low toxicity, may be safely used for bonding of tissues and possess a rapid cure rate and sufficient bonding power.

Claims

1. A surgical adhesive, which comprises at least one NCO-terminated hydrophilic urethane prepolymer, derived from (a) an organic polyisocyanate component comprising at least one fluorine-containing polyisocyanate and (b) a polyol component comprising at least one hydrophilic polyether polyol having an oxyethylene content of at least 30%.

2. The adhesive of claim 1, wherein said fluorine-containing polyisocyanate is at least one member selected from the group consisting of fluorine-containing aliphatic polyisocyanates and fluorine-containing cycloaliphatic polyisocyanates.

3. The adhesive of claim 1, wherein said fluorine-containing polyisocyanate is at least one member selected from the group consisting of fluorine-containing diisocyanates of the formulas (1) and (2):

space="preserve" listing-type="equation">OCN--Rf--NCO (1)

space="preserve" listing-type="equation">OCN--CH.sub.2 --Rf--CH.sub.2 --NCO (2)

wherein Rf is a perfluoroalkylene group containing 1 to 20 carbon atoms and up to 10 ether linkages

4. The adhesive of claim 3, wherein said perfluoroalkylene group is at least one member selected from the group consisting of --CF_2n,--CF₂ CF₂ OCF₂ --, --CF₂ O(CF₂)_m OCF₂ --,--CF(CF₃)O(CF₂)_m OCF(CF₃)--, and --CF₂ CF₂ OCF₂ CF(CF₃)O(CF₂)_m OCF(CF₃)CF₂ OCF₂ CF₂ --, wherein n is an integer of 1 to 20, and m is an integer of 1 to 10.

5. The adhesive of claim 1, wherein said polyisocyanate component comprises 2,2,3,3,4,4,5,5,-octafluorohexamethylene diisocyanate.

6. The adhesive of claim 1, wherein said polyisocyanate component further comprises up to 80% by weight of at least one polyisocyanate selected from the group consisting of aromatic polyisocyanates containing 6 to 20 carbon atoms, aliphatic polyisocyanates containing 2 to 18 carbon atoms, alicyclic polyisocyanates containing 4 to 15 carbon atoms, araliphatic polyisocyanates containing 8 to 15 carbon atoms, not including carbon atoms in NCO groups, and derivatives thereof containing one or more groups selected from the group consisting of urethane, carbodiimide, allophanate, urea, biuret, urethdione, urethimine, isocyanurate and oxazolidone groups.

7. The adhesive of claim 1, wherein said prepolymer has an isocyanate-content of 1 to 10% by weight.

8. The adhesive of claim 1, wherein said polyol component has an oxyethylene content of at least 30%.

9. The adhesive of claim 1, wherein said polyol component has an average equivalent weight of 100 to 5,000 and an average number of hydroxyl groups of 2 to 8.

10. The adhesive of claim 1, wherein said hydrophilic polyether polyol is at least one adduct of ethylene oxide or a combination thereof with one or more other alkylene oxides with at least one compound containing two or more active hydrogen atoms.

11. The adhesive of claim 10, wherein said compound containing two or more active hydrogen atoms is at least one member selected from the group consisting of polyhydric alcohols, polyhydric phenols, amines, polycarboxylic acids and phosphorous acids.

12. The adhesive of claim 1, wherein said hydrophilic polyether polyol is at least one member selected from the group consisting of polyoxyethylene polyols, polyoxyethylene/oxypropylene polyols and polyoxyethylene/oxybutylene polyols.

13. The adhesive of claim 1, wherein said polyol component further comprises at least one polyol selected from the group consisting of low molecular weight polyols, hydrophobic polyether polyols and polyester polyols.

14. The adhesive of claim 1, wherein said prepolymer is obtained by reacting said polyisocyanate component with said polyol component in such an amount to obtain a NCO/OH ratio of 1.5 to 5.0.

15. The adhesive of claim 1, which further comprises at least one unsaturated cyano compound containing a cyano group directly bonded to a polymerizable double bond.

16. The adhesive of claim 15, which comprises 20 to 90% by weight of said prepolymer and 10 to 80% by weight of said cyano compound.

17. The adhesive of claim 15, wherein said cyano compound is at least one member selected from the group consisting of cyanoacrylic acid, cyanomethacrylic acid, cyanoacrylates, cyanomethacrylates, acrylonitrile, methacrylonitrile, cyanoacrylonitrile, and cyanomethacrylonitrile.

18. The adhesive of claim 15, wherein said cyano compound is at least one member selected from the group consisting of methyl cyanoacrylate, ethyl cyanoacrylate, and iso-butyl cyanoacrylate.

19. The adhesive of claim 1, which further comprises up to 20% by weight of at least one additive selected from the group consisting of carbon black, metal oxides, silicates, acrylic resin powders, ceramic powders, softening agents, stabilizers, and physiologically active materials.

20. The adhesive of claim 19, wherein said physiologically active material is selected from the group consisting of antimicrobials, local anesthetics, antihistamines, antiphlogosis analgestics, antibiotics, astringents, vitamins, antifungal agents, peripheral nervous system anesthetics, vasodilators, hormones, crude drug essences, tinctures, crude drug powders and hypotensive agents.