Anti-bleed compounds, compositions and methods for use thereof

Abstract

The invention is based on the discovery that addition of certain carboxylic acid derivatives of siloxanes to thermosetting adhesive compositions and die-attach pastes renders such compositions and pastes extremely resistant to resin bleed. The present invention provides siloxane-carboxylic acid compounds useful as anti-bleed additives. Also provided are adhesive compositions and pastes containing the compounds of the invention, which are particularly useful in applications that require little to no resin bleed prior to curing of the compositions (such as e.g., electronic packaging applications).

1 - 25 . (canceled) 
     
     
         26 . An adhesive composition comprising:
 a) a quantity of an anti-bleed agent sufficient to reduce resin bleed upon application of the adhesive composition to a substrate, wherein the compound is selected from the group consisting of compounds I, II, III, IV, V and VI, or a salt thereof, having the formulae:   
       
         
           
           
               
               
           
         
         wherein:
 each of R and R 1  is independently selected from the group consisting of a C 1 -C 8  alkyl and phenyl; 
 R 2  is selected from the group consisting of a straight or a branched chain alkyl, a substituted alkyl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, a cycloalkyl, a substituted cycloalkyl, an aromatic, a substituted aromatic, a heterocyclic, a substituted heterocyclic, a heteroaromatic and a substituted heteroaromatic; 
 R 3  is selected from the group consisting of hydrogen and methyl; 
 R 4  is selected from the group consisting of a straight or a branched chain alkyl, a substituted alkyl, an aromatic and a substituted aromatic; 
 n is an integer having the value between 3 and 500; 
 m is an integer having the value between 0 and 100; 
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         b) at least one curing initiator. 
       
     
     
         27 . The adhesive composition of claim  1 , wherein R is methyl. 
     
     
         28 . The adhesive composition of  claim 26 , wherein R 1  is butyl. 
     
     
         29 . The adhesive composition of  claim 26 , wherein R is methyl and R 1  is butyl. 
     
     
         30 . The adhesive composition of  claim 26 , wherein: R 2  is selected from the group consisting of optionally substituted methyl, ethyl, ethenyl, methylethenyl, n-propyl, isopropyl, propenyl, butyl, isobutyl, sec-butyl, tert-butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, octyl, or octenyl; ethylallyl, ethyloctenyl, ethyldodecenyl, ethyloctadecenyl, cyclohexane, cyclohexene, bicyclohexene, norbornenyl, phenyl, or naphthyl. 
     
     
         31 . The adhesive composition of  claim 26 , wherein R 2  has the formula (CH 2 ) m  R 5  (R 6 ) m , wherein R 5  is a heteroatom, R 6  is optionally substituted alkyl, and each m is independently 1-12. 
     
     
         32 . The adhesive composition of  claim 26 , wherein R 2  is optionally substituted methyl, ethyl, ethenyl, n-propyl, isopropyl, propenyl, butyl, isobutyl, sec-butyl, tert-butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, octyl, or octenyl. 
     
     
         33 . The adhesive composition of  claim 26 , wherein R 2  is maleimide, cyclohexane, cyclohexene, bicyclohexene, or benzoic acid 
     
     
         34 . The adhesive composition of  claim 26 , wherein R 2  has the formula (CH 2 ) m  R 4 (R 5 ) m :
 wherein   R 4  is a heteroatom;   R 5  is optionally substituted alkyl; and   each m is independently 1-12.   
     
     
         35 . The adhesive composition of  claim 26 , wherein the anti-bleed agent is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         36 . The adhesive composition of  claim 26 , wherein the anti-bleed agent has the formula: 
       
         
           
           
               
               
           
         
         wherein: 
         each R and R 1  is independently C 1  to C 8  alkyl or phenyl; 
         X is a cation selected from ammonium, alkyl ammonium, dialkyl ammonium, trialkyl ammonium, tetraalkyl ammonium, cycloalkyl ammonium, aryl ammonium, substituted aryl ammonium, pyridinium, substituted pyridinium, or a mono-valent or poly-valent metal cation selected from lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, copper, zinc, aluminum, tin, or bismuth; 
         L is C 2  to C 10  alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, naphthyl; 
         n is to 500; and 
         m is 0 to 100; 
       
     
     
         37 . The adhesive composition of  claim 26 , wherein
 R 2  is C 4 -C 12  straight or branched chain alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, heteroaromatic, or substituted heteroaromatic, and   n is at least about 10 to at least about 250.   
     
     
         38 . The compound of  claim 26 , wherein R 2  comprises at least one vinyl group. 
     
     
         39 . The adhesive compositions of  claim 26 , further comprising a thermosetting resin. 
     
     
         40 . The adhesive composition of  claim 39 , wherein the thermosetting resin is selected from the group consisting of an epoxy, a phenolic, a phenolic novalac, a cresolic novalac, a polyurethane, a polyimide, a polyamide, a monomaleimide, a bismaleimide, a polymaleimide, an oxetane, an oxazoline, a benzoxazine, a resole, a maleimide, a cyanate ester, an acrylic, an acrylate, a methacrylate, a polyacrylate, a maleate, a fumarate, an itaconate, a vinyl ester, a vinyl ether, a cyanoacrylate, a styrenic, a polyvinyl alcohol, a polyester, a polyurea, a polysiloxane, and combinations thereof. 
     
     
         41 . The adhesive composition of  claim 39 , wherein the anti-bleed agent comprises about 0.01 to about 5.0 weight percent. 
     
     
         42 . A die-attach paste adhesive composition comprising:
 a) 2 weight percent to about 98 weight percent (wt %) of a thermosetting resin;   b) the adhesive composition of  claim 39 , wherein the adhesive composition comprises 0.1 wt % to about 5 wt % of the at least one curing initiator, based on total weight of the;   c) 0 to about 90 wt % of a filler;   d) 0.1 wt % to about 5 wt %, of at least one coupling agent, based on total weight of the paste.   
     
     
         43 . A method for attaching a first article to a second article, comprising:
 a) applying the adhesive composition of  claim 39  to the first article;   b) bringing the first and the second article into contact to form an assembly, wherein the first article and the second article are separated only by the adhesive composition applied in a); and thereafter,   c) subjecting the assembly to conditions suitable to cure the invention adhesive composition.   
     
     
         44 . The method of claim  24 , wherein the first and second articles are reversibly attached. 
     
     
         45 . A method for attaching a first semiconductor die to a second semiconductor die, including the steps of:
 a) providing a first die having a topside and an underside;   b) applying the die-attach paste of  claim 42  to the underside of the first die;   c) juxtaposing the first die and the second die such that the die-attach paste is an interface between the underside of the first die and the topside of the second die; and   d) curing the die-attach paste, thereby attaching a first semiconductor die to a second semiconductor die.