Surgical adhesive

• US 5,173,301 A
• Filed: 11/27/1991
• Issued: 12/22/1992
• Est. Priority Date: 11/27/1990
• Status: Expired due to Term

• Current Assignee: Sanyo Chemical Industries Limited
• Original Assignee: Sanyo Chemical Industries Limited
• Inventors: Matsuda, Takehisa, Itoh, Tetsuo
• Primary Examiner(s): Page, Thurman K.
• Assistant Examiner(s): BROUILLETTE, D GABRIELLE
• Application Number:
  US07/799,322
• Time in Patent Office: 391 Days
• Field of Search: 424/448, 424/445, 528/904, 528/905, 528/70, 523/118
• US Class Current: 424/448
• CPC Class Codes: A61L 24/046 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds A61L24/043 takes precedence
• 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 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/4018 Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/42 Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/425 the polyols containing one or two ether groups
• CPC Class Codes: C08G 18/4252 derived from polyols containing polyether groups and polycarboxylic acids
• CPC Class Codes: C08G 18/4607 having halogens
• CPC Class Codes: C08G 18/773 halogens
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C09J 175/06 from polyesters
• CPC Class Codes: Y10S 528/904 Isocyanate polymer having stated hydrophilic or hydrophobic property
• CPC Class Codes: Y10S 528/905 Polymer prepared from isocyanate reactant has adhesive property

Abstract

Surgical adhesives, comprising an NCO-terminated hydrophilic urethane prepolymer derived from an organic polyisocyanate and a polyol component comprising a polyester polyol derived from an electron-attracting group-containing dicarboxylic acid, such as 2-ketoglutaric acid, are capable of being easily hydrolyzed within a living body after a certain period of time.

Claims

1. A surgical adhesive which comprises at least one NCO-terminated hydrophilic urethane prepolymer, derived from (a) an organic polyisocyanate and (b) a polyol component comprising at least one polyester polyol derived from a dicarboxylic acid represented by the general formula:

space="preserve" listing-type="equation">HOOC--(A).sub.m --COOH (1)

wherein m is 0 or 1, A is --CH₂ -- or an electron attracting group represented by the formula;

--R--CO-- or ##STR2## R is a divalent hydrocarbon group containing 1-8 carbon atoms, R'"'"' is a divalent hydrocarbon group or halogen-substituted hydrocarbon group containing 1-8 carbon atoms, X is a halogen atom or nitro or cyano group, Y is hydrogen atom, a halogen atom or nitro or cyano group, n is 0, 1 or 2, wherein the polyester polyols derived from a dicarboxylic acid have an equivalent weight of 20-1000, the ratio of NCO/OH is 1.5 or more, and the NCO content of the NCO-terminated hydrophilic urethane prepolymer is 1-10%.

2. The adhesive of claim 1, wherein said dicarboxylic acid is at least one dicarboxylic acid selected from the group consisting of oxalic acid, alpha-keto-carboxylic acids and fluorine-containing dicarboxylic acids of the formula:

HOOC--(CH₂)_n'"'"' (CF₂)_m'"'"' --(CH₂)_n'"'"' --COOH wherein n'"'"' is 0, 1 or 2 and m'"'"' is an integer of at least 1.

3. The adhesive of claim 1, wherein said dicarboxylic acid comprises 2-ketoglutaric acid.

4. The adhesive of claim 1, wherein said polyol component further comprises a hydrophilic polyether polyol.

5. The adhesive of claim 4, wherein said polyol component comprises 10-90% by weight of said polyester polyol and 10-90% by weight of said hydrophilic polyether polyol.

6. The adhesive of claim 4, wherein said hydrophilic polyether polyol contains oxyethylene groups.

7. The adhesive of claim 4, wherein said hydrophilic polyether polyol is a polyoxyethylene diol or a polyoxyethylene/oxypropylene diol.

8. The adhesive of claim 1, wherein said polyester polyol contains oxyethylene groups.

9. The adhesive of claim 1, wherein said polyol component has an oxyethylene content of 30-90% by weight.

10. The adhesive of claim 1, wherein said polyol component has an equivalent weight of 200-3000.

11. The adhesive of claim 1, wherein said polyisocyanate comprises a fluorine-containing polyisocyanate.

12. The adhesive of claim 11, wherein said fluorine-containing polyisocyanate is at least one polyisocyanate selected from the group consisting of fluorine-containing diisocyanates of the formula (2) or (3):

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

space="preserve" listing-type="equation">OCN--CH.sub.2 --Rf--CH.sub.2 --NCO (3)

wherein Rf is a perfluoroalkylene group containing 1 to 20 carbon atoms and 0 to 10 ether linkages.

13. The adhesive of claim 1, wherein said prepolymer is obtained by reacting said polyisocyanate with said polyol component in such an amount providing NCO/OH ratio of 1.6-5.

14. The adhesive of claim 1, wherein said prepolymer has an NCO-content of 2-8% by weight.

15. The adhesive of claim 1, which contains 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 mateials.

16. The adhesive of claim 15, wherein the physiologically active material is selected from the group consisting of agents affecting central nervous system, antiallergic agents, cardiovascular agents, agents affecting respiratory organs, agents affecting digestive organs, hormone preparations, agents affecting metabolism, antitumor agents, antibiotic preparations, chemotherapeutics, antimicrobias, local anesthetics, antihistaminics, antiphlogistics, astringents, vitamins, antifungal agents, peripheral nervous anesthetics, vasodilators, and hypotensive agents.

17. A method for surgical bonding of tissue, which comprises applying the surgical adhesive of claim 1.

18. The method of claim 17, wherein said tissue is vascular vessel, heart, lung, windpipe, esophagus, stomach, kidney, small intestine, large intestine, rectum, liver, pancreas, spleen, nerve or skin.

19. The adhesive of claim 15, wherein the physiologically active material is selected from the group consisting of crude drug essences, tinctures and crude drug powders.