Adhesive composition , process for producing the same, adhesive film made with the same, substrate for semiconductor mounting, and semiconductor device

Abstract

The present invention provides an adhesive composition which comprises (a) an epoxy resin, (b) a curing agent and (c) a polymer compound incompatible with said epoxy resin, and further optionally comprises (d) a filler and/or (e) a curing accelerator; a process for producing an adhesive composition, comprising: mixing (a) the epoxy resin and (b) the curing agent with (d) the filler, followed by mixing the resultant mixture with (c) the polymer compound incompatible with the epoxy resin; an adhesive film comprising the above-mentioned adhesive composition formed into a film; a substrate for mounting semiconductor comprising a wiring board and the above-mentioned adhesive film disposed thereon on its side where chips are to be mounted; and a semiconductor device which comprises the above-mentioned adhesive film or the substrate for mounting semiconductor.

1 . An adhesive composition which comprises 
 (a) an epoxy resin;    (b) a curing agent; and    (c) a polymer compound incompatible with said epoxy resin.    
     
     
         2 . The adhesive composition according to  claim 1 , wherein a ratio of A/B is 0.24 to 1.0, where A represents a total weight of (a) the epoxy resin and (b) the curing agent and B represents a weight of (c) the polymer compound incompatible with the epoxy resin.  
     
     
         3 . The adhesive composition according to  claim 1  or  2 , wherein (a) the epoxy resin is a solid epoxy resin having a softening point of 50° C. or more as measured by a ring and ball method.  
     
     
         4 . The adhesive composition according to any one of  claims 1  to  3 , wherein (a) the epoxy resin has no mutagen.  
     
     
         5 . The adhesive composition according to any one of  claims 1  to  4 , wherein (b) the curing agent is a phenolic resin having a hydroxyl equivalent of 150 g/eq or more.  
     
     
         6 . The adhesive composition according to  claim 5 , wherein (b) the curing agent is a phenolic resin represented by the following general formula (I):  
       
         
           
           
               
               
           
         
         wherein R 1  each may be the same or different from each other and represents a hydrogen atom, a straight or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom; n represents an integer of 1 to 3; and m represents an integer of 0 to 50.  
       
     
     
         7 . The adhesive composition according to  claim 6 , wherein the phenolic resin represented by general formula (I) has a water absorption of 2% by volume or less.  
     
     
         8 . The adhesive composition according to any one of  claims 1  to  7 , wherein (c) the polymer compound incompatible with the epoxy resin is a functional group-containing acrylic copolymer.  
     
     
         9 . The adhesive composition according to  claim 6 , wherein the functional group-containing acrylic copolymer is an epoxy group-containing acrylic copolymer.  
     
     
         10 . The adhesive composition according to  claim 9 , wherein the epoxy group-containing acrylic copolymer contains 0.5 to 6% by weight of glycidyl acrylate or glycidyl methacrylate as a starting material therefor.  
     
     
         11 . The adhesive composition according to any one of  claims 8  to  10 , wherein the functional group-containing acrylic copolymer has a weight average molecular weight of 100,000 or more.  
     
     
         12 . The adhesive composition according to any one of  claims 8  to  11 , wherein the functional group-containing acrylic copolymer has a glass transition temperature of −50° C. to 30° C.  
     
     
         13 . The adhesive composition according to any one of  claims 1  to  12 , which further comprises (d) a filler.  
     
     
         14 . The adhesive composition according to  claim 13 , wherein (d) the filler has an average particle diameter of 0.005 μm to 0.1 μm.  
     
     
         15 . The adhesive composition according to  claim 13  or  14 , wherein (d) the filler is silica.  
     
     
         16 . The adhesive composition according to any one of  claims 13  to  15 , wherein (d) the filler has a surface coated with an organic substance.  
     
     
         17 . The adhesive composition according to any one of  claims 13  to  16 , wherein (d) the filler exhibits a contact angle with water of 0 to 100 degrees.  
     
     
         18 . The adhesive composition according to any one of  claims 13  to  17 , wherein (c) the polymer compound is an epoxy group-containing acrylic copolymer with a weight average molecular weight of 100,000 or more which contains 1.5 to 2.5% by weight of glycidyl acrylate or glycidyl methacrylate, wherein the adhesive composition contains 1 to 50 parts by volume of (d) the inorganic filler with an average particle diameter of 0.010 μm to 0.1 μm based on 100 parts by volume of the resin.  
     
     
         19 . The adhesive composition according to any one of  claims 1  to  18 , which further comprises (e) a curing accelerator.  
     
     
         20 . The adhesive composition according to  claim 19 , wherein (e) the curing accelerator is an imidazole compound.  
     
     
         21 . An adhesive composition wherein the components of the adhesive composition are separated into two phases after being cured as viewed in the cross-section thereof.  
     
     
         22 . The adhesive composition according to  claim 21 , wherein the two phases comprise a sea phase and an islands phase, wherein, a length of an outer periphery of the islands phase represented by S and an area of a cross-section represented by V satisfy a relationship represented by the following formula (1):  
       S/{square root}{square root over ( )}V>3.6  (1).  
     
     
         23 . An adhesive composition which comprises giving a cured product having a storage elastic modulus at 240° C. of 1 to 20 MPa.  
     
     
         24 . An adhesive composition which comprises having pores with an average diameter of 0.01 μm to 2 μm after being cured and a volume percentage of the pores in the composition is 0.1 to 20% by volume.  
     
     
         25 . The adhesive composition according to any one of  claims 1  to  20 , which satisfies at least one of the following requirements (i) to (iii): 
 (i) the components of the adhesive composition are separated into two phases after being cured as viewed in the cross-section thereof;  
 (ii) the adhesive composition gives a cured product having a storage elastic modulus at 240° C. of 1 to 20 MPa; and  
 (iii) the adhesive composition has pores having an average diameter of 0.01 μm to 2 μm after being cured and a volume percentage of the pores is 0.1 to 20% by volume.  
 
     
     
         26 . A process for producing an adhesive composition, which comprises mixing (a) an epoxy resin and (b) a curing agent with (d) a filler, followed by mixing the resultant mixture with (c) a polymer compound incompatible with the epoxy resin.  
     
     
         27 . An adhesive film comprising the adhesive composition according to any one of  claims 1  to  25  formed into a film.  
     
     
         28 . The adhesive film according to  claim 27 , which satisfies at least one of the following requirements (i) to (iii): 
 (i) the components of the adhesive film are separated into two phases after being cured as viewed in the cross-section thereof;    (ii) the adhesive film gives a cured product having a storage elastic modulus at 240° C. of 1 to 20 MPa; and    (iii) the adhesive film has pores having an average diameter of 0.01 μm to 2 μm after being cured and a volume percentage of the pores is 0.1 to 20% by volume.    
     
     
         29 . An adhesive film comprising a laminated cured product of an adhesive composition and a polyimide film, wherein the laminated cured product has a peel strength of 50 N/m or more as measured at 240° C.  
     
     
         30 . An adhesive film which comprises a laminated cured product of an adhesive composition and a polyimide film, and when the laminated cured product is subjected to moisture absorption treatment followed by heat treatment at 260° C. for 120 seconds, the laminated cured product does not suffer peeling with a diameter of 2 mm or more.  
     
     
         31 . An adhesive film which comprises having pores with an average diameter of 0.01 μm to 2 μm and a volume percentage of the pores is 0.1 to 20% by volume.  
     
     
         32 . An adhesive film which comprises exhibiting lowering in flow after 72 hours at 60° C. of 50% or less.  
     
     
         33 . An adhesive film which comprises components thereof being separated into two phases after being cured as viewed in the cross-section thereof.  
     
     
         34 . The adhesive film according to  claim 33 , wherein the two phases comprise a sea phase and an islands phase, wherein a length of an outer periphery of the islands phase represented by S and an area of a cross-section represented by V satisfy a relationship represented by the following formula (1):  
       S/{square root}{square root over ( )}V>3.6  (1).  
     
     
         35 . The adhesive film according to  claim 33  or  34 , wherein a cured product of an adhesive composition comprises (a) an epoxy resin, (b) a curing agent, (c) a polymer compound incompatible with the epoxy resin, and optionally (d) a filler and/or (e) a curing accelerator.  
     
     
         36 . The adhesive film according to any one of  claims 33  to  35 , wherein the film comprises: 
 49.5 to 17.0% by weight of the sum of (a) the epoxy resin and (b) the curing agent;  
 50.0 to 70.0% by weight of (c) the polymer compound;  
 0.45 to 10.0% by weight of (d) the filler; and  
 0.05 to 3.0% by weight of (e) the curing accelerator.  
 
     
     
         37 . The adhesive film according to  claim 36 , wherein a ratio of (a) the epoxy resin to (b) the curing agent is  33 : 67  to 75:25.  
     
     
         38 . An adhesive film having a support which comprises the adhesive film(s) according to  claim 27  is/are laminated on one surface or both surfaces of the support layer directly or through another layer.  
     
     
         39 . The adhesive film having a support according to  claim 38 , which further comprises, on one surface or both surfaces thereof, a layer or layers for protecting the adhesive layer.  
     
     
         40 . An adhesive film having a support which comprises the adhesive films according to  claim 27  being formed on both surfaces of a film having a glass transition temperature of 200° C. or more.  
     
     
         41 . A substrate for mounting semiconductor which comprises the adhesive film according to any one of  claims 27  to  40  being disposed on a wiring board on which chips are to be mounted.  
     
     
         42 . A semiconductor device which comprises the adhesive film according to any one of  claims 27  to  40  being used.  
     
     
         43 . A semiconductor device which comprises the substrate for mounting semiconductor according to  claim 41  being used.  
     
     
         44 . A semiconductor device which comprises a semiconductor chip being mounted on a wiring board for mounting a semiconductor through the adhesive film having a support according to any one of  claims 38  to  40 .  
     
     
         45 . A semiconductor device which comprises a plurality of semiconductor chips being mounted on one surface or both surfaces of a wiring board for mounting a semiconductor through the adhesive film having a support according to any one of  claims 38  to  40 .  
     
     
         46 . The semiconductor device according to  claim 44  or  45 , wherein the wiring board for mounting a semiconductor is an organic substrate.  
     
     
         47 . The semiconductor device according to any one of  claims 42  to  46 , wherein the device has no peeling with a diameter of 1 mm or more between the adhesive layer and the semiconductor chip after being subjected to moisture absorption treatment at 85° C., a relative humidity of 85% for 168 hours, followed by being passed through a reflow furnace at 260° C. for 120 seconds.  
     
     
         48 . A wiring board for mounting semiconductor which comprises the adhesive film having a support according to any one of  claims 38  to  40  being equipped with on a surface of the wiring board on which chips are to be mounted.