Thermosetting resin compositions containing maleimide and/or vinyl compounds

Abstract

In accordance with the present invention, there are provided novel thermosetting resin compositions which do not require solvent to provide a system having suitable viscosity for convenient handling. Invention compositions have the benefit of undergoing rapid cure. The resulting thermosets are stable to elevated temperatures, are highly flexible, have low moisture uptake and are consequently useful in a variety of applictions, e.g., in adhesive applications since they display good adhesion to both the substrate and the device attached thereto.

That which is claimed is:  
     
         1 . A bismaleimide composition having the structure:  
       
         
           
           
               
               
           
         
         wherein: 
 m 1, 2 or 3,  
 each R is independently selected from hydrogen or lower alkyl, and  
 X is a monovalent or polyvalent radical selected from: 
 branched chain alkyl, alkylene or alkylene oxide species having from about 12 to about 500 carbon atoms,  
 aromatic groups having the structure:  
                     
 
 wherein: 
 n=1, 2 or 3,  
 each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and  
 Z is a branched chain alkyl, alkylene or alkylene oxide species having from about 12 to about 500 atoms in the backbone thereof,  
 or mixtures thereof.  
 
 
       
     
     
         2 . A thermosetting resin composition comprising: 
 (a) a maleimide composition having the structure:                          wherein: 
 m=1, 2 or 3,  
 each R is independently selected from hydrogen or lower alkyl, and  
 X is a monovalent or polyvalent radical selected from: 
 branched chain alkyl, alkylene or alkylene oxide species having from about 12 to about 500 carbon atoms,  
 aromatic groups having the structure:  
                     
 
 wherein: 
 n=1, 2 or 3,  
 each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having, in the range of 3 up to 10 carbon atoms, and  
 Z is a branched chain alkyl, alkylene or alkylene oxide species having from about 12 to about 500 atoms in the backbone thereof,  
 or mixtures thereof;  
 
   (b) in the range of 0.2 up to 3 wt % of at least one free radical initiator, based on the total weight of the composition; and    (c) optionally, a diluent for the bismaleimide composition.    
     
     
         3 . The thermosetting resin composition according to  claim 2 , further comprising 
 (d) in the range of 0.1 up to 10 wt % of at least one coupling agent, based on the total weight of the composition.    
     
     
         4 . The thermosetting resin composition according to  claim 3 , wherein the composition has a viscosity of from about 10 to about 12,000 centipoise.  
     
     
         5 . The thermosetting resin composition according to  claim 3 , wherein the composition has a viscosity of from about 10 to about 2,000 centipoise.  
     
     
         6 . The thermosetting resin composition according to  claim 3 , wherein the diluent is selected from dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, xylene, methylene chloride, tetrahydrofuran, glycol ethers, methyl ethyl ketone or monoalkyl or dialkyl ethers of ethylene glycol, polyethylene glycol, propylene glycol or polypropylene glycol.  
     
     
         7 . The thermosetting resin composition according to  claim 3 , wherein the free radical initiator is selected from peroxides or azo compounds.  
     
     
         8 . The thermosetting resin composition according to  claim 3 , wherein the coupling agent is selected from silicate esters, metal acrylate salts, titanates or compounds containing a co-polymerizable group and a chelating ligand.  
     
     
         9 . A thermosetting resin composition comprising: 
 (a) a maleimide having the structure:                          wherein: 
 m 1, 2 or 3,  
 each R is independently selected from hydrogen or lower alkyl, and  
 X′ is selected from: 
 saturated straight chain alkyl, alkylene or alkylene oxide, or branched chain alkyl, alkylene or alkylene oxide, optionally containing saturated cyclic moieties as substituents on said alkyl, alkylene or alkylene oxide chain or as part of the backbone of the alkyl, alkylene or alkylene oxide chain, wherein said species have at least 6 carbon atoms,  
 aromatic groups having the structure:  
                     
 
 wherein 
 n=1, 2 or 3,  
 each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and  
 Z′ is selected from: 
 saturated straight chain alkyl, alkylene or alkylene oxide, or branched chain alkyl, alkylene or alkylene oxide, optionally containing saturated cyclic moieties as substituents on said alkyl, alkylene or alkylene oxide chain or as part of the backbone of the alkyl, alkylene or alkylene oxide chain, wherein said species have at least 6 carbon atoms,  
 siloxanes having the structure:  
 —(CR 2 ) m′ —[Si(R′) 2 —O] q′ —Si(R′) 2 —(CR 2 ) n′ — 
  wherein each R is independently defined as above, and each R′ is independently selected from hydrogen, lower alkyl or aryl, m′ falls in the range of 1 up to 10, n′ falls in the range of 1 up to 10, and q′ falls in the range of 1 up to 50,  
 polyalkylene oxides having the structure:  
 —[(CR 2 ) r —O—] q′ —(CR 2 ) s — 
  wherein each R is independently as defined above, r falls in the range of 1 up to 10, s falls in the range of 1 up to 10, and q′ is as defined above,  
 aromatic moieties having the structure:  
                     
  wherein each R is independently as defined above, t falls in the range of 2 up to 10, u is 1, 2 or 3, and Ar is as defined above,  
 polysiloxanes having the structure:  
 —(CR 2 ) m′ —[Si(R′) 2 —O—] q —Si(R′) 2 —(CR 2 ) n′ — 
  wherein each R and R′ is independently defined as above, and wherein each of m′, n′ and q is as defined above,  
 polyalkylene oxides having the structure:  
 —[(CR 2 ) r —O—] q′ —(CR 2 ) s — 
  wherein each R is independently as defined above, and wherein each of r, s and q′ is as defined above,  
 as well as mixtures of any two or more thereof,  
 
 
   (b) in the range of about 0.01 up to about 10 equivalents of a vinyl compound per equivalent of maleimide, wherein said vinyl compound has the structure:    YQ 0,1 -CR═CHR] q   (II)     wherein: 
 q is 1, 2 or 3,  
 each R is independently as defined above,  
 each Q is independently selected from —O—, —O—C(O)—, —C(O)— or —C(O)—O—, and  
 Y is selected from: 
 saturated straight chain alkyl, alkylene or alkylene oxide, or branched chain alkyl, alkylene or alkylene oxide, optionally containing saturated cyclic moieties as substituents on said alkyl, alkylene or alkylene oxide chain or as part of the backbone of the alkyl, alkylene or alkylene oxide chain, wherein said species have at least 6 carbon atoms,  
 aromatic moieties having the structure:  
                     
  wherein each R is independently as defined above, and each of Ar, t and u is as defined above,  
 siloxanes having the structure:  
 —(CR 2 ) m′ —[Si(R′) 2 —O] q —Si(R′) 2 —(CR 2 ) n′ — 
  wherein each R and R′ is independently defined as above, and wherein each of m′, n′ and q is as defined above,  
 polyalkylene oxides having the structure:  
 —[(CR 2 ) r —O—] q′ —(CR 2 ) s — 
  wherein each R is independently as defined above, and wherein each of r, s and q′ is as defined above,  
 as well as mixtures of any two or more thereof,  
 
   (c) in the range of 0.2 up to 3 wt % of at least one free radical initiator, based on the total weight of the composition.    
     
     
         10 . A thermosetting resin composition according to  claim 9  further comprising 
 (d) in the range of 0.1 up to 10 wt % of at least one coupling agent, based on the total weight of the composition.  
 
     
     
         11 . A thermosetting resin composition according to  claim 10  wherein X′ is a polyvalent radical selected from: 
 branched chain alkylene species having from about 12 to about 500 carbon atoms,  
 aromatic groups having the structure:  
                     
 wherein 
 n=1, 2 or 3,  
 each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and  
 Z′ is a branched chain alkyl, alkylene or alkylene oxide species having from about 12 to about 500 carbon atoms,  
 or mixtures thereof.  
 
 
     
     
         12 . A thermosetting resin composition in accordance with  claim 10  wherein Y is a polyvalent radical selected from: 
 branched chain alkylene or alkylene oxide species having from about 12 to about 500 carbon atoms,  
 aromatic groups having the structure:  
                     
  wherein 
 n=1, 2 or 3,  
 each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and  
 Z″ is a branched chain alkylene or alkylene oxide species having from about 12 to about 500 carbon atoms,  
 or mixtures thereof.  
 
 
     
     
         13 . A thermosetting resin composition according to  claim 12  wherein Q is —C(O)—O—.  
     
     
         14 . A thermosetting resin composition according to  claim 10  wherein X′ is derived from a dimer amine, and includes —(CH 2 ) 9 —CH(C 8 H 17 )—CH(C 8 H 17 )—(CH 2 ) 9 —.  
     
     
         15 . A thermosetting resin composition according to  claim 10  wherein Y is selected from stearyl, behenyl, eicosyl, isoeicosyl, as well as: 
 —O—[(CH 2 ) 2 —O—] 4 —, —(CH 2 ) 4 —O—(C 3 N 3 )—[O—(CH 2 ) 4 ] 2 —, wherein —(C 3 N 3 )— is a 2,4,6-trisubstituted 1,3,5-triazine;  
                     
  wherein —Ar— is a 1,3-disubstituted phenyl ring;  
 Y is derived from a dimer amine, and includes —(CH 2 ) 9 —CH(C 8 H 17 )—CH(C 8 H 17 )—(CH 2 ) 9 —;  
 optionally hydrogenated α,ω-disubstituted polybutadienes, optionally hydrogenated α,ω-disubstituted polyisoprenes, optionally hydrogenated α,ω-disubstituted poly[(1-ethyl)-1,2-ethane].  
 
     
     
         16 . A thermosetting resin composition according to  claim 11  wherein X′ and Y are not both aromatic.  
     
     
         17 . A thermosetting resin composition according to  claim 9 , wherein the free radical initiator is selected from peroxides or azo compounds.  
     
     
         18 . A thermosetting resin composition according to  claim 10  wherein the coupling agent is selected from silicate esters, metal acrylate salts, titanates or compounds containing a co-polymerizable group and a chelating ligand.  
     
     
         19 . A polyvinyl composition having the structure:  
       YQ 0,1 -CR═CHR] q   (II)  wherein: 
 q is 1, 2 or 3,  
 each R is independently selected from hydrogen or lower alkyl,  
 Q is —C(O)—O—, and  
 Y is selected from: 
 branched chain alkylene or alkylene oxide species having from about 12 to about 500 carbon atoms,  
 aromatic groups having the structure:  
                     
 
 wherein 
 n=1, 2 or 3,  
 each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and  
 Z is a branched chain alkylene or alkylene oxide species having from about 12 to about 500 carbon atoms,  
 or mixtures thereof.  
 
   
     
     
         20 . A thermosetting resin composition comprising 
 (a) a divinyl composition according to  claim 19 , and    (b) a sufficient amount of at least one free radical initiator.    
     
     
         21 . The thermosetting resin composition in accordance with  claim 20 , further comprising 
 (c) a sufficient amount of at least one coupling agent, based on the total weight of the composition.    
     
     
         22 . The thermosetting resin composition in accordance with  claim 20 , wherein the free radical initiator is selected from peroxides or azo compounds.  
     
     
         23 . The thermosetting resin composition in accordance with  claim 21 , wherein the coupling agent is selected from silicate esters, metal acrylate salts, titanates or compounds containing a copolymerizable group and a chelating ligand.  
     
     
         24 . An assembly comprising a first article permanently adhered to a second article by a cured aliquot of the thermosetting resin composition according to  claim 3 .  
     
     
         25 . An assembly comprising a first article permanently adhered to a second article by a cured aliquot of the thermosetting resin composition according to  claim 10 .  
     
     
         26 . An assembly comprising a first article permanently adhered to a second article by a cured aliquot of the thermosetting resin composition according to  claim 19 .  
     
     
         27 . A die-attach paste comprising: 
 in the range of about 10 up to 80 wt % of the thermosetting resin composition according to  claim 3 , and    in the range of about 20 up to 90 wt % of a conductive filler.    
     
     
         28 . A die-attach paste comprising: 
 in the range of about 10 up to 80 wt % of the thermosetting resin composition according to  claim 10 , and    in the range of about 20 up to 90 wt % of a conductive filler.    
     
     
         29 . A die-attach paste comprising: 
 in the range of about 10 up to 80 wt % of the thermosetting resin composition according to  claim 19 , and    in the range of about 20 up to 90 wt % of a conductive filler.    
     
     
         30 . A die-attach paste according to  claim 27  wherein the conductive filler is electrically conductive.  
     
     
         31 . A die-attach paste according to  claim 28  wherein the conductive filler is electrically conductive.  
     
     
         32 . A die-attach paste according to  claim 29  wherein the conductive filler is electrically conductive.  
     
     
         33 . A die-attach paste according to  claim 27  wherein said conductive filler is thermally conductive.  
     
     
         34 . A die-attach paste according to  claim 28  wherein said conductive filler is thermally conductive.  
     
     
         35 . A die-attach paste according to  claim 29  wherein said conductive filler is thermally conductive.  
     
     
         36 . An assembly comprising a microelectronic device permanently adhered to a substrate by a cured aliquot of the die attach paste according to  claim 27 .  
     
     
         37 . An assembly comprising a microelectronic device permanently adhered to a substrate by a cured aliquot of the die attach paste according to  claim 28 .  
     
     
         38 . An assembly comprising a microelectronic device permanently adhered to a substrate by a cured aliquot of the die attach paste according to  claim 29 .  
     
     
         39 . A method for adhesively attaching a first article to a second article, said method comprising: 
 (a) applying composition according to  claim 27  to said first article,    (b) bringing said first and second article into intimate contact to form an assembly wherein said first article and said second article are separated only by the adhesive composition applied in step (a), and thereafter,    (c) subjecting said assembly to conditions suitable to cure said adhesive composition.    
     
     
         40 . A method for adhesively attaching a first article to a second article, said method comprising: 
 (a) applying composition according to  claim 28  to said first article,    (b) bringing said first and second article into intimate contact to form an assembly wherein said first article and said second article are separated only by the adhesive composition applied in step (a), and thereafter,    (c) subjecting said assembly to conditions suitable to cure said adhesive composition.    
     
     
         41 . A method for adhesively attaching a first article to a second article, said method comprising: 
 (a) applying composition according to  claim 29  to said first article,    (b) bringing said first and second article into intimate contact to form an assembly wherein said first article and said second article are separated only by the adhesive composition applied in step (a), and thereafter,    (c) subjecting said assembly to conditions suitable to cure said adhesive composition.    
     
     
         42 . A method for adhesively attaching a microelectronic device to a substrate, said method comprising: 
 (a) applying die attach paste according to  claim 27  to said substrate and/or said microelectronic device,    (b) bringing said substrate and said device into intimate contact to form an assembly wherein said substrate and said device are separated only by the die attach composition applied in step (a), and thereafter,    (c) subjecting said assembly to conditions suitable to cure said die attach composition.    
     
     
         43 . A method for adhesively attaching a microelectronic device to a substrate, said method comprising: 
 (a) applying die attach paste according to  claim 28  to said substrate and/or said microelectronic device,    (b) bringing said substrate and said device into intimate contact to form an assembly wherein said substrate and said device are separated only by the die attach composition applied in step (a), and thereafter,    (c) subjecting said assembly to conditions suitable to cure said die attach composition.    
     
     
         44 . A method for adhesively attaching a microelectronic device to a substrate, said method comprising: 
 (a) applying die attach paste according to  claim 29  to said substrate and/or said microelectronic device,    (b) bringing said substrate and said device into intimate contact to form an assembly wherein said substrate and said device are separated only by the die attach composition applied in step (a), and thereafter,    (c) subjecting said assembly to conditions suitable to cure said die attach composition.    
     
     
         45 . Method for the preparation of bismaleimides from diamines, said method comprising: 
 adding diamine to a solution of maleic anhydride,    adding acetic anhydride to said solution once diamine addition is complete, and then allowing the resulting mixture to stir for at least 12 hours, and thereafter    treating the resulting reaction mixture with a suitable isomerizing agent.