Solid cyanoacrylate adhesive composition and method for its use

Abstract

A solid cyanoacrylate adhesive composition is disclosed which can be applied to a substrate in solid form and which polymerizes into an adhesive polymer upon liquifying. Preferably the solid cyanoacrylate composition liquefies at temperatures slightly above room temperature and polymerizes upon liquification. ξ-caprolactones are used as a solidifying polymer with cyanoacrylate monomers and other additives to form the solid cyanoacrylate adhesive composition. The solid cyanoacrylate adhesive composition is easy to apply, especially stable in solid form and is capable of use in a variety of industrial, consumer and medical applications.

What is claimed is:  
     
         1 . An adhesive composition which comprises at least one cyanoacrylate monomer and at least one solidifying polymer, wherein the adhesive composition is capable of polymerizing to form an adhesive polymer and wherein, before such polymerizing, the adhesive composition has a liquifying point within a specified temperature range and wherein the specified temperature range is from about 10° C. to about 60° C. and wherein such polymerizing does not substantially occur until the adhesive composition is liquefied.  
     
     
         2 . A composition according to  claim 1  wherein the specified temperature range is from about 30° C. to about 45° C.  
     
     
         3 . A composition according to  claim 1  where in the specified temperature range is from about 20° C. to about 40° C.  
     
     
         4 . A composition according to  claim 1  where in the specified temperature range is from about 25° C. to about 40° C.  
     
     
         5 . A composition according to  claim 1  wherein the cyanoacrylate monomer has the following structural formula:  
       
         
           
           
               
               
           
         
       
       Where R represents a substituted or unsubstituted constituent group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl, alkaryl, aralkyl, aryl, and carbalkoxy alkyl groups.  
     
     
         6 . A composition according to  claim 1  wherein R is selected from the group consisting of methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl, pentyl, neo-pentyl, hexyl, η-octyl, allyl, methallyl, crotyl, propargyl, cyclohexyl, benzyl, phenyl, cresyl, 2-chlorobutyl, trifluoroethyl, 2-methoxyethyl, 3-methoxybutyl, 2-ethoxy ethyl and 2-propoxethyl.  
     
     
         7 . A composition according to  claim 1  wherein the cyanoacrylate monomer is selected from the group consisting of methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, butyl 2-cyanoacrylate, and isobutyl 2-cyanoacrylate.  
     
     
         8 . A composition according to any one of claims  1 ,  2 ,  3 ,  4 ,  5 ,  6  or  7  wherein the solidifying polymer comprises a poly(ε-caprolactone).  
     
     
         9 . A composition according to any one of claims  1 ,  2 ,  3 ,  4 ,  5 ,  6 , or  7  wherein the solidifying polymer comprises a structure of the following formula:  
       
         
           
           
               
               
           
         
       
       wherein n is an integer.  
     
     
         10 . A composition according to  claim 9  wherein the composition also comprises a bioabsorbable material selected from the group consisting of monomers or oligomers of glycolides, lactides, ε-caprolactones, dixoanone, trimethylene carbonates, and copolymers of any of the foregoing with cyanoacrylates.  
     
     
         11 . A composition according to  claim 9  wherein the composition also comprises an additive selected form the group consisting of acrylates, methacrylates, acrylonitrile copolymers, crown ethers, sila crown ethers, calizarenes, esters of diabasic acids, perfumes, dyes, pigments, x-ray opacifiers, antimicrobial agents, antibiotics, growth promoting factors, drugs and fillers.  
     
     
         12 . A method for adhering two or more surfaces together, said method comprising: 
 a) applying to at least one surface an adhesive composition which comprises at lease one cyanoacrylate monomer and at least one solidifying polymer, wherein the adhesive composition is applied to said at least one surface in a solid form to create a layer of the adhesive composition on said at least one surface, wherein the adhesive composition is capable of polymerizing to form an adhesive polymer, and such polymerizing does not substantially occur until the adhesive composition is liquefied;    b) bringing the surfaces to be adhered into contact with each other such that the layer of adhesive composition is between the surfaces to be adhered; and    c) heating the layer of the adhesive composition such that the layer liquefies and polymerizes into an adhesive polymer.    
     
     
         13 . A method according to  claim 12  wherein the adhesive composition liquefies at a temperature in the range of from about 10° C. to about 60° C.  
     
     
         14 . A method according to  claim 12  wherein the adhesive composition liquefies at a temperature in the range of from about 20° C. to about 40° C.  
     
     
         15 . A method according to  claim 12  wherein the adhesive composition liquefies at a temperature in the range of from about 25° C. to about 40° C.  
     
     
         16 . A method according to  claim 12  wherein the cyanoacrylate monomer has the following structural formula:  
       
         
           
           
               
               
           
         
       
       where R represents a substituted or unsubstituted constituent group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl, alkaryl, aralkyl, aryl, and carbalkoxy alkyl groups.  
     
     
         17 . A method according to  claim 12  wherein R is selected from the group consisting of methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl, pentyl, neo-pentyl, hexyl, η-octyl, allyl, methallyl, crotyl, propargyl, cyclohexyl, benzyl, phenyl, cresyl, 2-chlorobutyl, trifluoroethyl, 2-methoxyethyl, 3-methoxybutyl, 2-ethoxy ethyl and 2-propoxyethyl.  
     
     
         18 . A method according to  claim 12  wherein the cyanoacrylate monomer is selected from the group consisting of methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, butyl 2-cyanoacrylate, and isobutyl 2-cyanoacrylate.  
     
     
         19 . A method according to any one of claims  12 ,  13 ,  14 ,  15 ,  16 ,  17  or  18  wherein the solidifying polymer comprises a poly(ε-caprolactone).  
     
     
         20 . A method according to any one of claims  12 ,  13 ,  14 ,  15 ,  16 ,  17  or  18  wherein the solidifying polymer comprises a structure of the following formula:  
       
         
           
           
               
               
           
         
       
       wherein n is an integer.  
     
     
         21 . A method according to  claim 20  wherein the composition also comprises a bioabsorbable material selected from the group consisting of monomers or oligomers of glycolides, lactides, ε-caprolactones, dixoanone, trimethylene carbonates, and copolymers of any of the foregoing with cyanoacrylates.  
     
     
         22 . A method according to  claim 20  wherein the composition also comprises an additive selected form the group consisting of acrylates, methacrylates, acrylonitrile copolymers, crown ethers, sila crown ethers, calizarenes, esters of diabasic acids, perfumes, dyes, pigments, x-ray opacifiers, antimicrobial agents, antibiotics, growth promoting factors, drugs and fillers.  
     
     
         23 . A method for coating a substrate with an adhesive coating, said method comprising: 
 a) applying to said substrate an adhesive composition which comprises at least one cyanoacrylate monomer and at least one solidifying polymer, wherein the adhesive composition is applied to said substrate in a solid form to create a layer of the adhesive composition on said substrate, wherein the adhesive composition is capable of polymerizing to form an adhesive polymer, and wherein such polymerizing does not substantially occur until the adhesive composition is liquefied; and    b) applying heat to the layer of the adhesive composition such that the layer liquefies and polymerizes into an adhesive polymer.    
     
     
         24 . A method according to  claim 23  wherein the adhesive composition liquefies at a temperature in the range of from 10° C. to about 60° C.  
     
     
         25 . A method according to  claim 23  wherein the adhesive composition liquefies at a temperature in the range of from 20° C. to about 40° C.  
     
     
         26 . A method according to  claim 23  wherein the adhesive composition liquefies at a temperature in the range of from 25° C. to about 40° C.  
     
     
         27 . A method according to  claim 23  wherein the cyanoacrylate monomer has the following structural formula:  
       
         
           
           
               
               
           
         
       
       where R represents a substituted or unsubstituted constituent group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl, alkaryl, aralkyl, aryl, and carbalkoxy alkyl groups.  
     
     
         28 . A method according to  claim 23  wherein R is selected from the group consisting of methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl, pentyl, neo-pentyl, hexyl, η-octyl, allyl, methallyl, crotyl, propargyl, cyclohexyl, benzyl, phenyl, cresyl, 2-chlorobutyl, trifluoroethyl, 2-methoxyethyl, 3-methoxybutyl, 2-ethoxy ethyl and 2-propoxyethyl.  
     
     
         29 . A method according to  claim 23  wherein the cyanoacrylate monomer is selected from the group consisting of methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, butyl 2-cyanoacrylate, and isobutyl 2-cyanoacrylate.  
     
     
         30 . A method according to any one of claims  23 ,  24 ,  25 ,  26 ,  27 ,  28  or  29  wherein the solidifying polymer comprises a poly(ε-caprolactone).  
     
     
         31 . A method according to any one of claims  23 ,  24 ,  25 ,  26 ,  27 ,  28  or  29  wherein the solidifying polymer comprises a structure of the following formula:  
       
         
           
           
               
               
           
         
       
       wherein n is an integer.  
     
     
         32 . A method according to  claim 31  wherein the composition also comprises a bioabsorbable material selected from the group consisting of monomers or oligomers of glycolides, lactides, ε-caprolactones, dixoanone, trimethylene carbonates, and copolymers of any of the foregoing with cyanoacrylates.  
     
     
         33 . A method according to  claim 31  wherein the composition also comprises an additive selected form the group consisting of acrylates, methacrylates, acrylonitrile copolymers, crown ethers, sila crown ethers, calizarenes, esters of diabasic acids, perfumes, dyes, pigments, x-ray opacifiers, antimicrobial agents, antibiotics, growth promoting factors, drugs and fillers.