Resin composition for non-conductive film with excellent high temperature properties for 3D TSV packaging

Abstract

The present disclosure relates to compositions for forming films and the use of said films in three-dimensional through silicon via (3D TSV) packages. In certain aspects, the present disclosure relates to compositions comprising one or more resins, one or more imidazoles with latent thermal activity, one or more inorganic fillers, and one or more additives, B-stage films prepared from the compositions of the present disclosure, and cured films obtained after curing the compositions of the present disclosure.

Description

[Technical field]

[0001] Aspects of the present disclosure relate to compositions for forming films and the use of said films in three-dimensional through silicon via (3D TSV) packages. In certain aspects, the present disclosure relates to compositions comprising one or more resins, one or more imidazoles with latent thermal activity, one or more inorganic fillers, and one or more additives, B-stage films prepared from the compositions of the present disclosure, and cured films obtained after curing of the compositions of the present disclosure. In certain aspects, the cured films obtained after curing of the compositions of the present disclosure have specific physical properties and / or combinations of physical properties. In certain aspects, the present disclosure relates to underfill films prepared from the compositions of the present disclosure, such as wafer level underfill films (WAUF). Film embodiments of the present disclosure are suitable for use in, for example, thermocompression bonding methods. [Background technology]

[0002] As we look towards the next generation of high performance 3D TSV packages, the materials industry is faced with the need to improve the high temperature properties of film materials (such as underfill film materials). Achieving this goal could bring benefits such as improved thermal stability and therefore improved reliability in applications across the automotive, computing, networking, and communications industries. Features that may be associated with improved high temperature properties of film materials include a relatively high Tg (glass transition temperature), a relatively low CTE (coefficient of thermal expansion), and a relatively high modulus of elasticity, for example at 250°C.

[0003] Problems have arisen when films prepared from certain conventional resin compositions containing maleimide-containing resins are used in thermocompression bonding processes. For example, in some cases, B-stage films prepared from certain conventional resin compositions containing maleimide-containing resins may have a DSC onset temperature of less than 100°C to 150°C. When such B-stage films are used in thermocompression bonding processes in which the bond head contact temperature is between 100°C and 150°C (e.g., when such processes have a bond head contact temperature between 130°C and 210°C), problems with material entrapment may occur during solder bonding. In other examples, B-stage films prepared from conventional resin compositions containing maleimide-containing resins may have a DSC onset temperature higher than the melting temperature of the solder (e.g., lead-free solder), e.g., a DSC onset temperature higher than 217°C. When such B-stage films are used in thermocompression bonding processes, problems with solder extrusion may occur in some cases. In some cases, solder extrusion problems can also occur when B-staged films prepared from conventional resin compositions that include one or more maleimide-containing resins have a ΔT from the DSC onset temperature to the DSC peak temperature that is greater than 20° C., such as about 40° C. Summary of the Invention [Problem to be solved by the invention]

[0004] Considering at least the considerations discussed above, there is interest in a composition comprising one or more resins, one or more inorganic fillers, and one or more additives, a B-stage film prepared from said composition, and a cured film obtained after curing said composition, wherein said composition comprises one or more imidazoles having potential thermal activity. As used herein, imidazoles having potential thermal activity refer to imidazoles that, when combined in an amount of 0.20 g with 1.0 g of NC-3000-L epoxy resin (Nippon Kayaku), produce a composition that exhibits a DSC onset temperature of at least 145° C. and a DSC peak temperature of at least 150° C. when measured with a TA Instruments Thermal Analyzer DSC Q20 at a ramp rate of 10° C. / min from room temperature to 300° C. in N2. For example, in some embodiments, the potentially thermally active imidazole, when analyzed as just described, exhibits a DSC onset temperature of at least 145° C., at least 150° C., at least 155° C., at least 160° C., at least 165° C., at least 170° C., at least 175° C., or at least 180° C. For example, in some embodiments, the potentially thermally active imidazole, when analyzed as just described, exhibits a DSC onset temperature of between 145° C. and 180° C., e.g., between 145° C. and 175° C., between 145° C. and 170° C., between 145° C. and 160° C., between 150° C. and 180° C., between 150° C. and 175° C., between 150° C. and 170° C., between 150° C. and 160° C., between 155° C. and 175° C., between 155° C. and 170° C., or between 155° C. and 165° C. In some embodiments, the potentially thermally active imidazole, when analyzed as just described, exhibits a DSC peak temperature of at least 150° C., at least 155° C., at least 160° C., at least 165° C., at least 170° C., at least 175° C., or at least 185° C. For example, in some embodiments, the potentially thermally active imidazole, when analyzed as just described, exhibits a DSC peak temperature of between 150° C. and 185° C., e.g., between 150° C. and 180° C., between 150° C. and 175° C., between 150° C. and 170° C., between 150° C. and 165° C., between 150° C. and 160° C., between 160° C. and 180° C., between 165° C. and 175° C., or between 160° C. and 170° C.

[0005] For the avoidance of doubt, it is to be understood that the DSC onset temperature and / or DSC peak temperature exhibited by a composition prepared and measured as described (i.e., a composition comprising 0.20 g of potentially thermally active imidazole and 1.0 g of NC-3000-L epoxy resin (Nippon Kayaku)) may be the same as or different from the DSC onset temperature and / or DSC peak temperature exhibited by a composition comprising the same potentially thermally active imidazole but containing other components such as one or more resins, or more inorganic fillers, and / or one or more additives.

[0006] In some embodiments, the potentially thermally active imidazole is a potentially thermally active encapsulated imidazole. As the term is used herein, a "latently thermally active encapsulated imidazole" is an imidazole that (a) is combined with an outer layer and / or barrier and (b) in an amount of 0.20 g, when combined with 1.0 g of NC-3000-L epoxy resin (Nippon Kayaku), produces a composition that exhibits a DSC onset temperature of at least 145° C. and a DSC peak temperature of at least 150° C., as measured on a TA Instruments Thermal Analyzer DSC Q20 at a ramp rate of 10° C. / min from room temperature to 300° C. in N2. For the avoidance of doubt, it is to be understood that when the potentially thermally active imidazole is a potentially thermally active encapsulated imidazole, the amount of 0.20 g refers to the amount of encapsulated imidazole (i.e., the amount of 0.20 g includes the amount of imidazole and coating).

[0007] In comparison, certain imidazoles do not constitute potentially thermally active imidazoles within the meaning of the present disclosure. Such imidazoles include those that, whether or not bound to an outer layer and / or barrier, when combined in an amount of 0.20 g with 1.0 g of NC-3000-L epoxy resin (Nippon Kayaku), produce a composition that exhibits a DSC onset temperature of less than 145° C. and a DSC peak temperature of less than 150° C. when measured on a TA Instruments Thermal Analyzer DSC Q20 at a ramp rate of 10° C. / min from room temperature to 300° C. in N2. For the avoidance of doubt, it is understood that an imidazole may not be a "potentially thermally active encapsulated imidazole" within the meaning of the present disclosure, even if it is encapsulated (i.e., bound to an outer layer and / or barrier), because it exhibits a DSC onset temperature of less than 145° C. and a DSC peak temperature of less than 150° C.

[0008] As a non-limiting example, four imidazoles were analyzed as above. Specifically, four separate experiments were performed. In each experiment, 0.20 g of either Imidazole A, Imidazole B, Imidazole C, or Imidazole D was mixed with 1.0 g of NC-3000-L epoxy resin (Nippon Kayaku), and the resulting composition was measured on a TA Instruments Thermal Analyzer DSC Q20 at a ramp rate of 10° C. / min from room temperature to 300° C. in N2. The DSC onset temperature and DSC peak temperature were measured. The results are shown in the table below. Imidazole A is 2-phenylimidazole. Imidazole B is 2-ethyl-4-methyl-1H-imidazole-1-propanenitrile. Since neither Imidazole A nor Imidazole B was bound to the outer layer and / or barrier, neither Imidazole A nor Imidazole B is a "potentially thermally active encapsulated imidazole" within the meaning of this disclosure. Imidazole C and Imidazole D were each encapsulated imidazoles with potential thermal activity of the type contemplated by the present disclosure.

[0009] [Table 1]

[0010] 1 Test conditions: 0.20 g of each imidazole was mixed with 1.0 g of NC-3000-L epoxy resin (Nippon Kayaku), and each resulting composition was analyzed using a TA Instruments thermal analyzer DSC Q20 at a ramp rate of 10 °C / min from room temperature to 300 °C in N2.

[0011] As shown above, when analyzed as described above, compositions containing imidazole A or imidazole B, respectively, exhibited a DSC onset temperature of less than 145° C. and a DSC peak temperature of less than 150° C., whereas compositions containing imidazole C or imidazole D, respectively, exhibited a DSC onset temperature of at least 145° C. and a DSC peak temperature of at least 150° C.

[0012] Thus, the above analysis provides a method for determining whether the imidazole associated with the outer layer and / or barrier constitutes a "potentially thermally active encapsulated imidazole" within the meaning of the present disclosure. If the composition exhibits a DSC onset temperature of at least 145° C. and a DSC peak temperature of at least 150° C. when subjected to the above analysis, the imidazole associated with the outer layer and / or barrier constitutes a "potentially thermally active encapsulated imidazole" within the meaning of the present disclosure. Conversely, if the composition exhibits a DSC onset temperature of less than 145° C. and a DSC peak temperature of less than 150° C., the imidazole associated with the outer layer and / or barrier does not constitute a "potentially thermally active encapsulated imidazole" within the meaning of the present disclosure.

[0013] The embodiments of the compositions of the present disclosure address the problems discussed above. For example, the embodiments of the underfill films prepared from the compositions of the present disclosure are suitable for thermocompression bonding methods, such as thermocompression bonding methods for 3D TSV stacking applications. Furthermore, the embodiments of the underfill films prepared from the compositions of the present disclosure exhibit one or more of good die corner coverage, gap filling, and electrical interconnect bond formation.

[0014] In some embodiments, aspects of the present disclosure are directed to the following: 1. one or more resins selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins; one or more imidazoles having potential thermal activity, one or more inorganic fillers, and one or more additives selected from the group consisting of adhesion promoters and film formers; A composition comprising: After the composition forms a film, the film has the following physical properties: Tg>200°C as measured by dynamic mechanical analysis (DMA); Storage modulus at 25℃ < 6.5GPa, Storage modulus at 250°C > 0.1 GPa, and Coefficient of thermal expansion (CTE) <250ppm / ℃, A composition comprising:

[0015] 2. The composition of embodiment 1, wherein said one or more potentially thermally active imidazoles are one or more encapsulated potentially thermally active imidazoles.

[0016] 3. The maleimide-containing resin

[0017] [ka]

[0018] (In the formula: Each R is independently selected from the group consisting of H and substituted or unsubstituted alkyl; each m is independently selected from the group consisting of 0, 1, 2, 3, or 4; n is 0, 1, 2, 3, 4 or 5. A compound represented by the formula: or

[0019] [ka]

[0020] (wherein n is 0, 1, 2, 3, 4 or 5). The compound represented by the formula: The composition of any of the preceding embodiments.

[0021] 4. The (meth)acrylic resin is

[0022] [ka]

[0023] (wherein n is 0, 1, 2, 3, 4 or 5). The composition of any of the preceding embodiments, wherein

[0024] 5. The epoxy resin is

[0025] [ka]

[0026] (In the formula, n is 0, 1, 2, 3, 4 or 5, and m is 0, 1, 2, 3, 4 or 5.) The composition of any of the preceding embodiments, wherein the compound is represented by:

[0027] 6. After the composition forms a film, the film has the following physical properties: Differential scanning calorimetry (DSC) onset temperatures between 120°C and 200°C, as measured by DSC at a ramp rate of 10°C / min, and Minimum film melt viscosity of 10 Pa·s to 10,000 Pa·s measured in N2 using a DHR2 rheometer at a ramp rate of 10°C / min; The composition of any of the preceding embodiments, having

[0028] 7. The composition of any of the preceding embodiments, wherein after the composition forms a film, the ΔT from the DSC onset temperature to the DSC peak temperature of the film is less than 20° C. or less than 15° C.

[0029] 8. The composition of any of the preceding embodiments, wherein after the composition forms a film, the ΔT from the DSC onset temperature to the DSC peak temperature of the film is less than 10° C. or less than 5° C.

[0030] 9. Preparing the composition of any of embodiments 1-8; casting the composition into a film; exposing the cast film to an elevated temperature to cure the film; A method for preparing a cured film comprising:

[0031] 10. One or more resins selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins; one or more imidazoles having potential thermal activity, one or more inorganic fillers, and one or more additives selected from the group consisting of adhesion promoters and film formers; preparing a composition comprising: casting the composition into a film; exposing the cast film to an elevated temperature to cure the film; A method for preparing a cured film comprising:

[0032] 11. The method of embodiment 10, wherein said one or more imidazoles with potential thermal activity are one or more encapsulated imidazoles with potential thermal activity.

[0033] 12. A cured film prepared according to the method of any of embodiments 9-11.

[0034] 13. The film has the following physical properties: Tg>200°C as measured by dynamic mechanical analysis (DMA); Storage modulus at 25℃ < 5.5GPa, Storage modulus at 250°C > 0.1 GPa, and Coefficient of thermal expansion (CTE) <250ppm / ℃, 12. A film prepared according to any one of embodiments 9 to 11, comprising:

[0035] 14. The film of embodiment 12 or embodiment 13, wherein the film is an underfill film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] The compositions and methods of the present disclosure may be more readily understood by reference to the following detailed description.

[0037] According to the present disclosure, there is provided a composition comprising one or more resins, one or more imidazoles with latent thermal activity, one or more inorganic fillers, and one or more additives. In some embodiments, the one or more resins are selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins. In some embodiments, the one or more additives are selected from the group consisting of adhesion promoters and film formers. In some embodiments, the one or more imidazoles with latent thermal activity are one or more encapsulated imidazoles with latent thermal activity.

[0038] Methods of encapsulating curing agents for use in chemical compositions to be cured are known in the art and are described, for example, in WO 2011 / 126702.

[0039] In some embodiments, the encapsulated imidazole (e.g., a potentially thermally active encapsulated imidazole) is an imidazole encapsulated in a polymer coating (e.g., the polymer coating forms a shell around the imidazole). In some embodiments, the polymer coating is resistant to thermal and / or chemical degradation. In some embodiments, the imidazole and / or the polymer coating can undergo a change in morphology and / or expansion in the presence of heat. In some embodiments, such a change in morphology is the result of melting, evaporation, and / or a change from a glassy to a rubbery and / or liquid state.

[0040] Non-limiting examples of imidazoles that may be encapsulated (to form an encapsulated imidazole, e.g., an encapsulated imidazole with latent thermal activity) include 2-methylimidazole (Imicure AMI-2), 2-phenylimidazole (Curezol 2PZ), 2-phenyl-4-methylimidazole (Curezol 2P4MZ), 2-heptadecylimidazole (Curezol C17Z), 2-phenyl-4,5-dihydroxymethylimidazole (Curezol 2PHZ-S), and Curzol 2MZ azine.

[0041] In some embodiments, the particle size of the encapsulated imidazole (e.g., encapsulated imidazole with latent thermal activity) is between 1 μm and 500 μm. In some embodiments, the particle size of the encapsulated imidazole (e.g., encapsulated imidazole with latent thermal activity) is between 1 μm and 250 μm. In some embodiments, the particle size of the encapsulated imidazole (e.g., encapsulated imidazole with latent thermal activity) is between 1 μm and 200 μm.

[0042] In some embodiments, the polymer coating used to encapsulate the imidazole is a crosslinked polymer or a high melting point polymer. In some embodiments, the polymer coating used to encapsulate the imidazole is selected from poly(p-xylylene) (parylene); crosslinked epoxy, such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol A epoxy novolac, bisphenol F epoxy novolac, 3,4 epoxy cyclohexyl methyl, 3,4 epoxy cyclohexyl carboxylate; crosslinked acrylate, such as hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tricyclodecane dimethanol diacrylate.

[0043] In some embodiments, the coating is applied by vapor deposition, an interfacial polymerization process, or a fluidized bed coating operation.

[0044] In some embodiments, after the composition forms a film, the film has certain characteristics and / or properties that make the film suitable for use in a thermocompression bonding process. For example, in some embodiments, after the composition forms a film, the film has a Tg>100°C, a storage modulus at 25°C<5GPa, a storage modulus at 250°C>0.1GPa, and a coefficient of thermal expansion (CTE)<250ppm / °C as measured by dynamic mechanical analysis (DMA). In some embodiments, after the composition forms a B-stage film, the B-stage film has a differential scanning calorimetry (DSC) onset temperature of 120°C-250°C and a minimum film melt viscosity of 10 Pa·s-10,000 Pa·s measured in N2 using a DHR2 rheometer with a ramp rate of 10°C / min, as measured by DSC at a 10°C / min ramp rate (e.g., 130°C-250°C).

[0045] In some embodiments, after the composition forms a cured film, the cured film has a Tg of >100°C, >125°C, >150°C, >160°C, >165°C, >170°C, >175°C, >180°C, >185°C, >190°C, >200°C, >210°C, >220°C, >230°C, >240°C, >250°C, >260°C, >270°C, >280°C, >290°C, or >300°C as measured by dynamic mechanical analysis (DMA). In some embodiments, after the composition forms a cured film, the cured film has a Tg of 100°C to 110°C, 110°C to 120°C, 120°C to 130°C, 130°C to 140°C, 140°C to 150°C, 150°C to 160°C, 160°C to 170°C, 170°C to 180°C, 180°C to 190°C, 190°C to 200°C, 200°C to 210°C, 210°C to 220°C, 220°C to 230°C, 230°C to 240°C, 240°C to 250°C, 250°C to 260°C, 260°C to 270°C, 270°C to 280°C, 280°C to 290°C, or 290°C to 300°C, as measured by DMA.

[0046] In some embodiments, after the composition forms a cured film, the cured film has a Tg of >100°C, >105°C, >110°C, >115°C, >120°C, >125°C, >130°C, >135°C, >150°C, >160°C, >170°C, >180°C, >190°C, >200°C, >210°C, >220°C, >230°C, >240°C, or >250°C as measured by thermomechanical analysis (TMA). In some embodiments, after the composition forms a cured film, the cured film has a Tg of 100° C. to 110° C., 110° C. to 120° C., 120° C. to 130° C., 130° C. to 140° C., 140° C. to 150° C., 150° C. to 160° C., 160° C. to 170° C., 170° C. to 180° C., 180° C. to 190° C., 190° C. to 200° C., 200° C. to 210° C., 210° C. to 220° C., 220° C. to 230° C., 230° C. to 240° C., or 240° C. to 250° C. In some embodiments, after the composition forms a cured film, the cured film has a Tg of 130° C. to 170° C., e.g., 130° C. to 160° C., or 130° C. to 150° C.

[0047] In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 25° C. of <3 GPa, <3.5 GPa, <4 GPa, <4.5 GPa, <5 GPa, <5.5 GPa, <6 GPa, or <6.5 GPa.

[0048] In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 25° C. of 2.0 GPa to 3.0 GPa, 3.0 GPa to 3.5 GPa, 3.5 GPa to 4.0 GPa, 4.0 GPa to 4.5 GPa, 4.5 GPa to 5.0 GPa, 5.0 GPa to 5.5 GPa, 5.5 GPa to 6.0 GPa, or 6.0 GPa to 6.5 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 25° C. of 3.0 GPa to 6.5 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 25° C. of 4.0 GPa to 5.5 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 25° C. of 4.0 GPa to 5.0 GPa.

[0049] In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 250° C. of >100 MPa, >125 MPa, >150 MPa, >175 MPa, >200 MPa, >225 MPa, or >250 MPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 250° C. of 100 MPa to 150 MPa, 100 MPa to 200 MPa, 150 MPa to 200 MPa, 100 MPa to 250 MPa, or 200 MPa to 250 MPa.

[0050] In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 230° C. of >100 MPa, >125 MPa, >150 MPa, >175 MPa, >200 MPa, >225 MPa, or >250 MPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 250° C. of 100 MPa to 150 MPa, 100 MPa to 200 MPa, 150 MPa to 200 MPa, 100 MPa to 250 MPa, or 200 MPa to 250 MPa.

[0051] In some embodiments, after the composition forms a cured film, the cured film has a coefficient of thermal expansion (CTE) of <50 ppm / ° C., <60 ppm / ° C., <70 ppm / ° C., <80 ppm / ° C., <90 ppm / ° C., <100 ppm / ° C., <110 ppm / ° C., <120 ppm / ° C., <130 ppm / ° C., <140 ppm / ° C., <150 ppm / ° C., <160 ppm / ° C., <170 ppm / ° C., <180 ppm / ° C., <190 ppm / ° C., <200 ppm / ° C., <210 ppm / ° C., <220 ppm / ° C., <230 ppm / ° C., <240 ppm / ° C., or <250 ppm / ° C.

[0052] In some embodiments, after the composition forms a cured film, the cured film has a coefficient of thermal expansion (CTE) above Tg of <100 ppm / °C, <110 ppm / °C, <120 ppm / °C, <130 ppm / °C, <140 ppm / °C, <150 ppm / °C, <160 ppm / °C, <170 ppm / °C, <180 ppm / °C, <190 ppm / °C, <200 ppm / °C, <210 ppm / °C, <220 ppm / °C, <230 ppm / °C, <240 ppm / °C, or <250 ppm / °C. In some embodiments, after the composition forms a cured film, the cured film has a coefficient of thermal expansion (CTE) above Tg of 50 ppm / °C to 80 ppm / °C. In some embodiments, after the composition forms a cured film, the cured film has a coefficient of thermal expansion (CTE) above Tg of 60 ppm / ° C. to 80 ppm / ° C. In some embodiments, after the composition forms a cured film, the cured film has a coefficient of thermal expansion (CTE) above Tg of 60 ppm / ° C. to 70 ppm / ° C.

[0053] In some embodiments, after the composition forms a B-stage film, the B-stage film has a minimum film melt viscosity, measured in N2 using a DHR2 rheometer at a ramp rate of 10°C / min, of 300 Pa·s to 6,000 Pa·s. In some embodiments, after the composition forms a B-stage film, the B-stage film has a minimum film melt viscosity, measured in N2 using a DHR2 rheometer at a ramp rate of 10°C / min, of 300 Pa·s to 3,000 Pa·s. In some embodiments, after the composition forms a B-stage film, the B-stage film has a minimum film melt viscosity, measured in N2 using a DHR2 rheometer at a ramp rate of 10°C / min, of 400 Pa·s to 2,000 Pa·s.

[0054] In some embodiments, after the composition forms a B-stage film, the B-stage film has a viscosity of 300 Pa·s to 400 Pa·s, 400 Pa·s to 500 Pa·s, 500 Pa·s to 600 Pa·s, 600 Pa·s to 700 Pa·s, 700 Pa·s to 800 Pa·s, 800 Pa·s to 900 Pa·s, 900 Pa·s to 1,000 Pa·s, 1,000 Pa·s to 1,100 Pa·s, 1,100 Pa·s to 1,200 Pa·s, 1,200 Pa·s to 1,300 Pa·s, 1,300 Pa·s to 1,400 Pa·s, 1,400 Pa·s to 1,500 Pa·s, 1,500 Pa·s to 1,600 Pa·s, or 1,800 Pa·s to 2,100 Pa·s. ,600Pa·s, 1,600Pa·s~1,700Pa·s, 1,700Pa·s~1,800Pa·s, 1,800Pa·s~1,900Pa·s, 1,900Pa ·s~2,000Pa·s, 2,000Pa·s~2,100Pa·s, 2,100Pa·s~2,200Pa·s, 2,200Pa·s~2,300Pa·s, 2,30 having a minimum film melt viscosity of 0 Pa·s to 2,400 Pa·s, 2,400 Pa·s to 2,500 Pa·s, 2,500 Pa·s to 2,600 Pa·s, 2,600 Pa·s to 2,700 Pa·s, 2,700 Pa·s to 2,800 Pa·s, 2,800 Pa·s to 2,900 Pa·s, or 2,900 Pa·s to 3,000 Pa·s.

[0055] In some embodiments, after the composition forms a B-stage film, the B-stage film has a differential scanning calorimetry (DSC) onset temperature of 120°C to 130°C, 120°C to 150°C, 120°C to 140°C, 130°C to 140°C, 140°C to 150°C, 160°C to 170°C, 170°C to 180°C, 180°C to 190°C, 190°C to 200°C, 200°C to 210°C, 210°C to 220°C, 220°C to 230°C, 230°C to 240°C, or 240°C to 250°C, as measured by DSC in N2 at a ramp rate of 10°C / min.

[0056] In some embodiments, after the composition forms a B-stage film, the B-stage film has a differential scanning calorimetry (DSC) onset temperature of about 120° C. to about 130° C., about 120° C. to about 150° C., about 120° C. to about 140° C., about 130° C. to about 140° C., about 140° C. to about 150° C., about 150° C. to about 160° C., about 160° C. to about 170° C., about 170° C. to about 180° C., about 180° C. to about 190° C., about 190° C. to about 200° C., about 200° C. to about 210° C., about 210° C. to about 220° C., about 220° C. to about 230° C., about 230° C. to about 240° C., or about 240° C. to about 250° C., as measured by DSC in N2 at a ramp rate of 10° C. / min.

[0057] In some embodiments, after the composition forms a B-stage film, the ΔT from the DSC onset temperature to the DSC peak temperature of the B-stage film is less than 20° C., less than 15° C., less than 10° C., or less than 5° C. In some embodiments, after the composition forms a B-stage film, the ΔT from the DSC onset temperature to the DSC peak temperature of the B-stage film is 0° C. to 5° C., 5° C. to 10° C., 10° C. to 15° C., or 15° C. to 20° C. In some embodiments, after the composition forms a B-stage film, the ΔT from the DSC onset temperature to the DSC peak temperature of the B-stage film is 0° C., 1° C., 2° C., 3° ​​C., 4° C., 5° C., 6° C., 7° C., 8° C., 9° C., 10° C., 11° C., 12° C., 13° C., 14° C., 15° C., 16° C., 17° C., 18° C., 19° C., or 20° C. Without wishing to be bound by theory, it is believed that a ΔT from the DSC onset temperature to the DSC peak temperature of less than 20° C., less than 15° C., less than 10° C., or less than 5° C., or between 0° C. and 5° C., 5° C. and 10° C., 10° C. and 15° C., or between 15° C. and 20° C., represents a fast cure rate, such as preventing the occurrence of solder extrusion (a phenomenon that, in at least some embodiments, renders the composition unsuitable or unsuitable for thermocompression bonding). Conversely, without wishing to be bound by theory, it is believed that a B-stage film having a ΔT from the DSC onset temperature to the DSC peak temperature of 20° C. or greater is not suitable for thermocompression bonding methods. For example, certain B-stage films prepared from compositions including bismaleimide resin, epoxy resin, and 4,4-diaminodiphenyl sulfone, but not including one or more potentially thermally active imidazoles (e.g., one or more encapsulated potentially thermally active imidazoles), are known to have a ΔT from the DSC onset temperature to the DSC peak temperature of 20° C. or greater, and, without wishing to be bound by theory, are believed to be unsuitable for thermocompression bonding processes.

[0058] In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 0.5% to 10% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 1% to 8% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 2% to 7% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 2.5% to 6.5% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 3% to 6% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 2.5% to 4.5% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 1% to 4% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 2% to 4% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 2% to 3.5% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 2% to 3% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from 2.5% to 3.5% by weight. In some embodiments, the one or more imidazoles with latent thermal activity referred to in this paragraph are one or more encapsulated imidazoles with latent thermal activity.

[0059] In some embodiments, the one or more imidazoles having latent thermal activity are included in an amount ranging from about 0.5% to about 10% by weight. In some embodiments, the one or more imidazoles having latent thermal activity are included in an amount ranging from about 1% to about 8% by weight. In some embodiments, the one or more imidazoles having latent thermal activity are included in an amount ranging from about 2% to about 7% by weight. In some embodiments, the one or more imidazoles having latent thermal activity are included in an amount ranging from about 2.5% to about 6.5% by weight. In some embodiments, the one or more imidazoles having latent thermal activity are included in an amount ranging from about 3% to about 6% by weight. In some embodiments, the one or more imidazoles having latent thermal activity are included in an amount ranging from about 2.5% to about 4.5% by weight. In some embodiments, the one or more imidazoles having latent thermal activity are included in an amount ranging from about 1% to about 4% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from about 2% to about 4% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from about 2% to about 3.5% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from about 2% to about 3% by weight. In some embodiments, the one or more imidazoles with latent thermal activity are included in an amount ranging from about 2.5% to about 3.5% by weight. In some embodiments, the one or more imidazoles with latent thermal activity referred to in this paragraph are one or more encapsulated imidazoles with latent thermal activity.

[0060] In some embodiments, the maleimide-containing resin, the nadimide-containing resin, or the itaconimide-containing resin may be represented as follows:

[0061] [ka]

[0062] During the ceremony, m is 1 to 15, p is 0-15, Each R 2 is halogen or C 1-6 independently selected from alkyl, J is a monovalent or polyvalent radical containing organic and / or organosiloxane groups.

[0063] In some embodiments, J is: - a hydrocarbyl or substituted hydrocarbyl species typically having in the range of from about 6 to about 500 carbon atoms, the hydrocarbyl species being selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl, arylalkynyl or alkynylaryl, with the proviso that X can be aryl only if X comprises a combination of two or more different species; - a hydrocarbylene or hydrocarbylene species typically having a range of from about 6 to about 500 carbon atoms, the hydrocarbylene species being selected from alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, arylene, alkylarylene, arylalkylene, arylalkenylene, alkenylarylene, arylalkynylene, or alkynylarylene; - Substituted or unsubstituted C6-C 10 Aryl, - heterocyclic or substituted heterocyclic species, typically having in the range of from about 6 to about 500 carbon atoms; - polysiloxane, - polysiloxane-polyurethane block copolymers, or - One or more of the above and a covalent bond, -O-, -S-, -NR-, -NR-C(O)-, -NR-C(O)-O-, -NR-C(O)-NR-, -SC(O)-, -SC(O)-O-, -SC(O)-NR-, -OS( O)2-, -OS(O)2-O-, -OS(O)2-NR-, -OS(O)-, -OS(O)-O-, -OS(O)-NR-, -O-NR-C(O)-, -O-NR-C(O)-O, -O-NR-C(O)-NR, - NR-OC(O)-, -NR-OC(O)-O-, -NR-OC(O)-NR-, -O-NR-C(S)-, -O-NR-C(S)-O-, -O-NR-C(S)-NR-, -NR-OC(S)-, -NR-OC(S )-O-, -NR-OC(S)-NR-, -OC(S)-, -OC(S)-O-, -OC(S)-NR-, -NR-C(S)-, -NR-C(S)-O-, -NR-C(S)-NR-, -SS(O)2-, -SS(O) 2- in combination with a linker selected from O-, -SS(O)2-NR-, -NR-OS(O)-, -NR-OS(O)-O-, -NR-OS(O)-NR-, -NR-OS(O)2-, -NR-OS(O)2-O-, -NR-OS(O)2-NR-, -O-NR-S(O)-, -O-NR-S(O)-O-, -O-NR-S(O)-NR-, -O-NR-S(O)2-O-, -O-NR-S(O)2-NR-, -O-NR-S(O)2-, -OP(O)R2-, -SP(O)R2-, or -NR-P(O)R2-; is a monovalent or polyvalent group selected from

[0064] In some embodiments, J is selected from the group consisting of substituted or unsubstituted C6 aryl, oxyalkyl, thioalkyl, aminoalkyl, carboxylalkyl, oxyalkenyl, thioalkenyl, aminoalkenyl, carboxyalkenyl, oxyalkynyl, thioalkynyl, aminoalkynyl, carboxyalkynyl, oxycycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxycycloalkyl, oxychloroalkenyl, thiocycloalkenyl, aminocycloalkenyl, carboxycycloalkenyl, heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyaryl, thioaryl, aminoaryl, carboxyaryl, heteroaryl, oxyheteroaryl, thioheteroaryl, aminoheteroaryl, carboxyheteroaryl, oxyalkylaryl, thioalkylaryl, aminoalkylaryl, carboxyalkylaryl, oxyarylalkyl, thioarylalkyl, aminoarylalkyl, carboxyarylalkyl, oxyarylalkenyl, thioarylalkenyl, aminoarylalkenyl, carboxyarylalkyl, oxyarylalkenyl, thioarylalkenyl, aminoarylalkenyl, carboxyarylalkyl, Diarylalkenyl, oxyalkenylaryl, thioalkenylaryl, aminoalkenylaryl, carboxyalkenylaryl, oxyarylalkynyl, thioarylalkynyl, aminoarylalkynyl, carboxyarylalkynyl, oxyalkynylaryl, thioalkynylaryl, aminoalkynylaryl or carboxyalkynylaryl, oxyalkylene, thioalkylene, aminoalkylene, carboxyalkylene, oxyalkenylene, thioalkenylene, aminoalkenylene, carboxyalkenylene alkynylene, oxyalkynylene, thioalkynylene, aminoalkynylene, carboxyalkynylene, oxycycloalkylene, thiocycloalkylene, aminocycloalkylene, carboxycycloalkylene, oxycycloalkenylene, thiocycloalkenylene, aminocycloalkenylene, carboxycycloalkenylene, oxyarylene, thioarylene, aminoarylene, carboxyarylene, oxyalkylarylene, thioalkylarylene, aminoalkylarylene, carboxyalkylarylene, oxyarylalkylene,thioarylalkylene, aminoarylalkylene, carboxyarylalkylene, oxyarylalkenylene, thioarylalkenylene, aminoarylalkenylene, carboxyarylalkenylene, oxyalkenylarylene, thioalkenylarylene, aminoalkenylarylene, carboxyalkenylarylene, oxyarylalkynylene, thioarylalkynylene, aminoarylalkynylene, carboxyarylalkynylene, oxyalkynylarylene, thioalkynylarylene, aminoalkynylarylene, carboxyalkynylarylene, heteroarylene, oxyheteroarylene, thioheteroarylene, aminoheteroarylene, carboxyheteroarylene, heteroatom-containing divalent or polyvalent cyclic moiety, oxyheteroatom-containing divalent or polyvalent cyclic moiety, thioheteroatom-containing divalent or polyvalent cyclic moiety, aminoheteroatom-containing divalent or polyvalent cyclic moiety, or carboxyheteroatom-containing divalent or polyvalent cyclic moiety.

[0065] In some embodiments, the maleimide-containing resin is represented by the following:

[0066] [ka]

[0067] During the ceremony, Each R is independently selected from the group consisting of H and substituted or unsubstituted alkyl; each m is independently selected from the group consisting of 0, 1, 2, 3, and 4; n is 0, 1, 2, 3, 4, and 5.

[0068] In some embodiments, the composition comprises a compound represented by the following formula:

[0069] [ka]

[0070] This compound is BMI-5100 (chemical name: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide; Daiwa Kasei, Japan), which has a number average molecular weight of about 300 as determined by gel permeation chromatography (GPC).

[0071] In some embodiments, the maleimide-containing resin is represented by the following:

[0072] [ka]

[0073] In the formula, n is 0, 1, 2, 3, 4 or 5.

[0074] In some embodiments, the maleimide-containing resin is a BMI resin having a maleimide equivalent weight of 180 to 400. Maleimide equivalent weight is the weight in grams of a resin containing one equivalent of maleimide functional groups. In some embodiments, the maleimide-containing resin is a BMI resin having a maleimide equivalent weight of 220. In some embodiments, the maleimide-containing resin is a BMI resin having a maleimide equivalent weight of 300. In some embodiments, the maleimide-containing resin is a BMI resin having a maleimide equivalent weight of about 400. In some embodiments, the maleimide-containing resin is a BMI resin having a maleimide equivalent weight of about 390 to about 400. In some embodiments, the maleimide-containing resin is a BMI resin having a maleimide equivalent weight of 390 to 400.

[0075] In some embodiments, the maleimide-containing resin is included in an amount ranging from about 1% to about 20% by weight. In some embodiments, the maleimide-containing resin is included in an amount ranging from about 1% to about 15% by weight. In some embodiments, the maleimide-containing resin is included in an amount ranging from about 3% to about 15% by weight. In some embodiments, the maleimide-containing resin is included in an amount ranging from about 1% to about 5% by weight. In some embodiments, the maleimide-containing resin is included in an amount ranging from about 5% to about 20% by weight. In some embodiments, the maleimide-containing resin is included in an amount ranging from about 5% to about 15% by weight. In some embodiments, the maleimide-containing resin is included in an amount ranging from about 10% to about 20% by weight. In some embodiments, the maleimide-containing resin is included in an amount ranging from about 10% to about 15% by weight. In some embodiments, the maleimide-containing resin is included in an amount ranging from about 12% to about 17% by weight. In some embodiments, the maleimide-containing resin is present at about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, or about 20% by weight.

[0076] In some embodiments, the itaconimide-containing resin is represented by the following:

[0077] [ka]

[0078] In the formula, Ar is a substituted or unsubstituted aryl group.

[0079] In some embodiments, the itaconimide-containing resin is:

[0080] [ka]

[0081] In some embodiments, the nadimide is represented by the following:

[0082] [ka]

[0083] During the ceremony, Ar is substituted or unsubstituted aryl; R is selected from the group consisting of H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

[0084] As mentioned above, the composition of the present disclosure includes one or more epoxy resins among other components. A wide variety of epoxy-functionalized resins are contemplated for use herein, such as liquid epoxy resins based on bisphenol A, solid epoxy resins based on bisphenol A, liquid epoxy resins based on bisphenol F (e.g., Epicron EXA-835LV), multifunctional epoxy resins based on phenol novolac resins, dicyclopentadiene-type epoxy resins (e.g., Epicron HP-7200L), naphthalene-type epoxy resins, and the like, as well as mixtures of any two or more thereof.

[0085] Exemplary epoxy-functionalized resins contemplated for use herein include diepoxides of cycloaliphatic alcohols, hydrogenated bisphenol A (commercially available as Epalloy 5000), difunctional cycloaliphatic glycidyl esters of hexahydrophthalic anhydride (commercially available as Epalloy 5200), Epicron EXA-835LV, Epicron HP-7200L, and the like, as well as mixtures of any two or more thereof.

[0086] In certain embodiments, the epoxy component may include a combination of two or more different bisphenol-based epoxies. These bisphenol-based epoxies may be selected from bisphenol A, bisphenol F, or bisphenol S epoxies, or combinations thereof. Additionally, two or more different bisphenol epoxies may be used within the same type of resin (such as A, F, or S).

[0087] Commercially available examples of bisphenol epoxies contemplated for use herein include bisphenol F type epoxies (RE-404-S from Nippon Kayaku Co., Ltd. (Japan), Epicron 830 (RE1801), 830S (RE1815), 830A (REI826), and 830W from Dainippon Ink and Chemicals, Inc., and RSL1738 and YL-983U from Resolution) and bisphenol A type epoxies (YL-979 and 980 from Resolution).

[0088] The above bisphenol epoxies, available commercially from Dainippon Ink and Chemicals, are advertised as liquid undiluted epichlorohydrin-bisphenol F epoxies with much lower viscosities than conventional epoxies based on bisphenol A epoxies, and have similar physical properties to liquid bisphenol A epoxies. The bisphenol F epoxies have lower viscosities than the bisphenol A epoxies, all else being the same between the two epoxies, resulting in lower viscosities and faster flowing underfill sealant materials. The EEW of these four bisphenol F epoxies is 165-180. Viscosities at 25°C are 3,000-4,500 cps (except for RE1801, which has a viscosity upper limit of 4,000 cps). Hydrolyzable chloride content is reported to be 200 ppm for RE1815 and 830W, and 100 ppm for RE1826.

[0089] The bisphenol epoxies available from Resolution and discussed above are advertised as low chloride content liquid epoxies. The bisphenol A epoxies have an EEW (g / eq) of 180-195 and a viscosity at 25°C of 100-250 cps. The total chloride content of YL-979 is reported to be 500-700 ppm, and the total chloride content of YL-980 is reported to be 100-300 ppm. The bisphenol F epoxies have an EEW (g / eq) of 165-180 and a viscosity at 25°C of 30-60. The total chloride content of RSL-1738 is reported to be 500-700 ppm, and the total chloride content of YL-983U is reported to be 150-350 ppm.

[0090] In addition to bisphenol epoxies, other epoxy compounds are contemplated for use as the epoxy component of the compositions of the present disclosure. For example, cycloaliphatic epoxies such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbonate can be used. Monofunctional, difunctional or multifunctional reactive diluents may also be used to adjust the viscosity and / or reduce the Tg of the resulting resin material. Examples of reactive diluents include butyl glycidyl ether, cresyl glycidyl ether, polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether, and the like.

[0091] Epoxies suitable for use herein include polyglycidyl derivatives of phenolic compounds, such as Epon 828, Epon 1001, Epon 1009, and Epon 1031, available under the tradename Epon from Resolution, Inc.; DER 331, DER 332, DER 334, and DER 542 from The Dow Chemical Company; and Blen-S from Nippon Kayaku Co., Ltd. Other suitable epoxies include polyepoxides prepared from polyols and the like, and polyglycidyl derivatives of phenol-formaldehyde novolacs, such as DEN 431, DEN 438, and DEN 439 from The Dow Chemical Company. Cresol analogs are available under the tradename Araldite, such as Araldite ECN 1235, Araldite ECN 1273, and Araldite ECN 1299 from Ciba Specialty Chemicals, Inc. SU-8 is a bisphenol A type epoxy novolac available from Resolution. Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in the present invention, commercially available resins include Glyamine 135, Glyamine 125, and Glyamine 115 from FIC; Araldite MY-720, Araldite 0500, and Araldite 0510 from Chiba Specialty Chemicals; and PGA-X and PGA-C from Sherwin-Williams.

[0092] Suitable monofunctional epoxy coreactant diluents for optional use herein include those having a viscosity lower than that of the epoxy component, typically less than about 250 cps. The monofunctional epoxy coreactant diluent may have an epoxy group having an alkyl group having from about 6 to about 28 carbon atoms, examples of which include C 6~28 Alkyl glycidyl ether, C 6~28 Fatty acid glycidyl ester, C 6~28 Alkylphenol glycidyl ether and the like.

[0093] In some embodiments, the epoxy resin is novolac epoxy EEW200, novolac epoxy EEW300, or novolac epoxy EEW140.

[0094] In some embodiments, the epoxy resin is a compound represented by the following formula:

[0095] [ka]

[0096] In the formula, n is 0, 1, 2, 3, 4 or 5; and m is 0, 1, 2, 3, 4 or 5.

[0097] In some embodiments, the epoxy resin is included in an amount ranging from about 1% to about 30% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 1% to about 25% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 1% to about 20% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 1% to about 15% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 3% to about 15% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 1% to about 5% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 5% to about 20% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 5% to about 15% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 10% to about 20% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 15% to about 30% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 15% to about 25% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 10% to about 15% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 10% to about 15% by weight. In some embodiments, the epoxy resin is included in an amount ranging from about 10% to about 11% by weight, about 12% by weight, about 13% by weight, about 14% by weight, about 15% by weight, about 16% by weight, about 17% by weight, about 18% by weight, about 19% by weight, about 20% by weight, about 21% by weight, about 22% by weight, about 23% by weight, about 24% by weight, about 25% by weight, about 26% by weight, about 27% by weight, about 28% by weight, about 29% by weight, or about 30% by weight.

[0098] In some embodiments, the film-forming binder resin is included in an amount ranging from about 1% to about 25% by weight. In some embodiments, the film-forming binder resin is included in an amount ranging from about 1% to about 20% by weight. In some embodiments, the film-forming binder resin is included in an amount ranging from about 5% to about 15% by weight. In some embodiments, the film-forming binder resin is included in an amount ranging from about 7% to about 12% by weight. In some embodiments, the film-forming binder resin is included in an amount ranging from about 9% to about 11% by weight. In some embodiments, the film-forming binder resin is included in an amount ranging from about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, or about 20% by weight.

[0099] The compositions of the present disclosure include, among other components, one or more (meth)acrylate-containing resins, as described above. In some embodiments, the (meth)acrylic resin is represented by the following:

[0100] [ka]

[0101] In the formula, n is 0, 1, 2, 3, 4 or 5.

[0102] In some embodiments, the (meth)acrylate-containing resin is included in an amount ranging from about 1% to about 20% by weight. In some embodiments, the (meth)acrylate-containing resin is included in an amount ranging from about 1% to about 15% by weight. In some embodiments, the (meth)acrylate-containing resin is included in an amount ranging from about 3% to about 15% by weight. In some embodiments, the (meth)acrylate-containing resin is included in an amount ranging from about 1% to about 5% by weight. In some embodiments, the (meth)acrylate-containing resin is included in an amount ranging from about 5% to about 20% by weight. In some embodiments, the (meth)acrylate-containing resin is included in an amount ranging from about 5% to about 15% by weight. In some embodiments, the (meth)acrylate-containing resin is included in an amount ranging from about 10% to about 20% by weight. In some embodiments, the (meth)acrylate-containing resin is included in an amount ranging from about 10% to about 15% by weight. In some embodiments, the (meth)acrylate-containing resin is included in an amount ranging from about 12% to about 17% by weight. In some embodiments, the (meth)acrylate-containing resin is included in an amount of about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, or about 20% by weight.

[0103] The composition of the present disclosure includes one or more inorganic fillers, among other components, as described above. In some embodiments, the filler is an electrically non-conductive filler, such as silica. In some embodiments, the filler is (or includes) silica, calcium silicate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, aluminum oxide (Al2O3), zinc oxide (ZnO), magnesium oxide (MgO), aluminum nitride (AlN), boron nitride (BN), carbon nanotubes, diamond, clay, aluminosilicate, and the like, as well as any mixture of two or more thereof.

[0104] In some embodiments, the inorganic filler is an inorganic non-conductive filler comprising particles having a maximum particle size of 5 μm or less than 5 μm. For example, in some embodiments, the filler has a particle size of about 0.1 μm to about 5 μm or 0.1 μm to 5 μm. In some embodiments, the loading of the filler is sufficient to meet the requirements of the underfill material. In some embodiments, the filler is included in an amount ranging from about 10% to about 70% by weight. In some embodiments, the filler is included in an amount ranging from about 20% to about 60% by weight. In some embodiments, the filler is included in an amount ranging from about 25% to about 55% by weight. In some embodiments, the filler is included in an amount ranging from about 30% to about 50% by weight. In some embodiments, the filler is included in an amount ranging from about 35% to about 45% by weight. In some embodiments, the filler is present at about 35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, or about 45% by weight.

[0105] The compositions of the present disclosure, as described above, include one or more additives selected from the group consisting of adhesion promoters and film formers, among other ingredients.

[0106] As used herein, the term "adhesion promoter" refers to compounds that enhance the adhesive properties of the formulations into which they are introduced. Adhesion promoters can be organic or inorganic compounds and can include combinations thereof. Non-limiting examples of adhesion promoters include organozirconate compounds, organotitanate compounds, and silane coupling agents. In some embodiments, the adhesion promoter is Dow's Z6040.

[0107] In some embodiments, the adhesion promoter is included in an amount ranging from about 0.1% to about 5% by weight. In some embodiments, the adhesion promoter is included in an amount ranging from about 0.1% to about 1.0% by weight. In some embodiments, the adhesion promoter is included in an amount ranging from about 0.5% to about 1.0% by weight. In some embodiments, the adhesion promoter is included in an amount ranging from about 0.5% to about 1.5% by weight. In some embodiments, the adhesion promoter is included in an amount ranging from about 1% to about 2% by weight, about 2% to about 3% by weight, about 3% to about 4% by weight, or about 4% to about 5% by weight.

[0108] As used herein, the term "film former" refers to a compound that aids in the formation of a film, such as by increasing the viscosity of the combined materials (as a non-limiting example). Non-limiting examples of film formers, including elastomer additive components, include, but are not limited to, copolymerized ethylene acrylic elastomers, natural or synthetic rubbers such as substituted polyethylene, resins such as polyvinyl butyral resins and chlorosulfonated polyethylene synthetic rubbers (CSM), partially crosslinked butyl rubber compounds such as butyl rubber products available under the brand names Carrara®, DPR®, Isolene® and Karen® from Royal Elastomer of New Jersey, and ethylene acrylic elastomer materials such as Vamac® available from DuPont. Further non-limiting examples of film formers include, but are not limited to, acrylic polymers (e.g., polymers containing glycidyl functional groups), such as butyl acrylate-ethyl acrylate-acetonitrile copolymers and ethyl acrylate-acetonitrile copolymers, such as copolymers available from Nagase JP.

[0109] In some embodiments, the film former is included in an amount ranging from about 15 to about 40% by weight. In some embodiments, the film former is included in an amount ranging from about 7.5 to about 30% by weight. In some embodiments, the film former is included in an amount ranging from about 20 to about 30% by weight. In some embodiments, the film former is included in an amount ranging from about 22 to about 28% by weight. In some embodiments, the film former is included in an amount ranging from about 23 to about 25% by weight. In some embodiments, the film former is included in an amount ranging from about 24%, about 25%, or about 26% by weight.

[0110] In some embodiments, the compositions of the present disclosure further comprise one or more fluxing agents.

[0111] As used herein, the term "fluxing agent" refers to a reducing agent that prevents oxides from forming on the surface of molten metal. Non-limiting examples of fluxing agents include compounds having at least one (meth)acrylate group and at least one carboxylic acid group, carboxylic acids (including but not limited to compounds having one or more acrylic acid functional groups, rosin gum, dodecanedioic acid (commercially available from Aldrich as Caufrey M2), adipic acid, sebacic acid, polybasic polyanhydrides, maleic acid, tartaric acid, citric acid, etc.), alcohols, hydroxyl acids and bases, polyols (including but not limited to ethylene glycol, glycerin, 3-[bis(glycidyloxymethyl)methoxy]-1,2-propanediol, D-ribose, D-cellobiose, cellulose, 3-cyclohexene-1,1-dimethanol, etc.).

[0112] In some embodiments, the fluxing agent is included in an amount ranging from about 1 to about 10% by weight. In some embodiments, the fluxing agent is included in an amount ranging from about 1 to about 5% by weight. In some embodiments, the fluxing agent is included in an amount ranging from about 5 to about 10% by weight. In some embodiments, the fluxing agent is included in an amount ranging from about 2 to about 8% by weight. In some embodiments, the fluxing agent is included in an amount ranging from about 3 to about 7% by weight. In some embodiments, the fluxing agent is included in an amount ranging from about 3 to about 5% by weight. In some embodiments, the fluxing agent is included in an amount ranging from about 3 to about 7% by weight. In some embodiments, the fluxing agent is included in an amount ranging from about 3 to about 7% by weight. In some embodiments, the fluxing agent is included in an amount of about 3%, about 4%, or about 5% by weight.

[0113] Embodiments of the present disclosure also relate to methods of preparing B-staged and / or cured films.

[0114] In some embodiments, a method of preparing a cured film includes: one or more resins selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins; one or more imidazoles having potential thermal activity, one or more inorganic fillers, and one or more additives selected from the group consisting of adhesion promoters and film formers; preparing a composition comprising: casting the composition into a film; exposing the cast film to an elevated temperature to cure the film; Includes.

[0115] In some embodiments, a method of preparing a cured film includes: one or more resins selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins; one or more encapsulated imidazoles having latent thermal activity, one or more inorganic fillers, and one or more additives selected from the group consisting of adhesion promoters and film formers; preparing a composition comprising: casting the composition into a film; exposing the cast film to an elevated temperature to cure the film; Includes.

[0116] In some embodiments, a method of preparing a cured film includes: one or more resins selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins; one or more imidazoles having potential thermal activity, one or more inorganic fillers, one or more additives selected from the group consisting of adhesion promoters and film formers; and one or more fluxing agents; preparing a composition comprising: casting the composition into a film; exposing the cast film to an elevated temperature to cure the film; Includes.

[0117] In some embodiments, a method of preparing a cured film includes: one or more resins selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins; one or more encapsulated imidazoles having latent thermal activity, one or more inorganic fillers, one or more additives selected from the group consisting of adhesion promoters and film formers; and one or more fluxing agents; preparing a composition comprising: casting the composition into a film; exposing the cast film to an elevated temperature to cure the film; Includes.

[0118] In some embodiments of the method of preparing a cured film, the one or more resins selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins are as disclosed elsewhere herein, and are optionally present in the amounts disclosed elsewhere herein.

[0119] In some embodiments of the method of preparing a cured film, the one or more imidazoles are as disclosed elsewhere herein, and are optionally present in the amounts disclosed elsewhere herein.

[0120] In some embodiments of the method of preparing a cured film, the one or more inorganic fillers are as disclosed elsewhere herein, and are optionally present in the amounts disclosed elsewhere herein.

[0121] In some embodiments of the method of preparing a cured film, one or more additives selected from the group consisting of adhesion promoters and film formers are disclosed elsewhere herein, and are optionally present in the amounts disclosed elsewhere herein.

[0122] In some embodiments of the method of preparing a cured film, the one or more fluxing agents are as disclosed elsewhere herein, and are optionally present in the amounts disclosed elsewhere herein.

[0123] In some embodiments of the method of preparing a cured film, the one or more fluxing agents are compounds having at least one (meth)acrylate group and at least one carboxylic acid group, optionally present in amounts disclosed elsewhere herein.

[0124] In some embodiments of the method of preparing a cured film, the one or more fluxing agents are one or more fluxing agents described herein, optionally present in the amounts disclosed elsewhere herein.

[0125] In some embodiments, the films prepared according to the methods for preparing a cured film disclosed herein have the physical properties of the films disclosed elsewhere herein. For example, in some embodiments, the films prepared according to the methods for preparing a film disclosed herein have one or more of the following properties disclosed elsewhere herein: Tg measured by DMA, storage modulus at 25° C., storage modulus at 230° C., storage modulus at 250° C., CTE, DSC onset temperature measured by DSC at a ramp rate of 10° C. / min, minimum film melt viscosity measured using a DHR2 rheometer at a ramp rate of 10° C. / min in N2.

[0126] In some embodiments, a film prepared according to the methods of preparing a film disclosed herein has the following physical properties: Tg>200°C as measured by dynamic mechanical analysis (DMA); Storage modulus at 25℃ < 5.5GPa, Storage modulus at 250°C > 0.1 GPa, and Coefficient of thermal expansion (CTE) <250ppm / ℃, has.

[0127] In some embodiments, a film prepared according to the methods of preparing a film disclosed herein has the following physical properties: Tg>230°C as measured by dynamic mechanical analysis (DMA); Storage modulus at 25℃ < 5GPa, Storage modulus at 230°C > 0.2 GPa, and Coefficient of thermal expansion (CTE) <150ppm / ℃, has.

[0128] In some embodiments, a film prepared according to the methods of preparing a film disclosed herein has the following physical properties: Tg>240°C as measured by dynamic mechanical analysis (DMA); Storage modulus at 25℃ < 4.8GPa, Storage modulus at 230°C > 0.25 GPa, and Coefficient of thermal expansion (CTE) <120ppm / ℃, has.

[0129] In some embodiments, a film prepared according to the methods of preparing a film disclosed herein has the following physical properties: Tg measured by dynamic mechanical analysis (DMA) is 230℃~280℃, Storage modulus at 25°C is 4.0GPa to 5.5GPa, and Storage modulus at 230℃ is 0.1GPa~0.4GPa, has.

[0130] In some embodiments, a film prepared according to the methods of preparing a film disclosed herein has the following physical properties: Tg measured by dynamic mechanical analysis (DMA) is 230℃~280℃, Storage modulus at 25℃ is 4.0GPa~5.5GPa, Storage modulus at 230℃ is 0.1GPa to 0.4GPa, and Minimum film melt viscosity of 300 Pa·s to 3,000 Pa·s measured in N2 using a DHR2 rheometer at a ramp rate of 10°C / min; having

[0131] In some embodiments, a film prepared according to the methods of preparing a film disclosed herein has the following physical properties: Tg measured by dynamic mechanical analysis (DMA) is 230℃~280℃, Storage modulus at 25℃ is 4.0GPa~5.0GPa, Storage modulus at 230℃ is 0.1GPa to 0.3GPa, and Coefficient of thermal expansion (CTE) is 20ppm / ℃~150ppm / ℃, has.

[0132] In some embodiments, a film prepared according to the methods of preparing a film disclosed herein has the following physical properties: Tg measured by dynamic mechanical analysis (DMA) is 230℃~280℃, Storage modulus at 25℃ is 4.0GPa~5.0GPa, Storage modulus at 230℃ is 0.2GPa~0.3GPa, Coefficient of thermal expansion (CTE) is 50ppm / ℃ to 125ppm / ℃, and Minimum film melt viscosity of 300 Pa·s to 2,000 Pa·s measured in N2 using a DHR2 rheometer at a ramp rate of 10°C / min; has. EXAMPLES

[0133] Exemplary embodiments including components of compositions according to the present invention are shown in Table 1, as well as the properties of those exemplary embodiments. Both Encapsulated Imidazole A and Encapsulated Imidazole B are encapsulated imidazoles with potential thermal activity within the meaning of the present disclosure.

[0134] [Table 2]

[0135] The components of four comparative compositions (not within the scope of this disclosure) (Comparative Examples 1-4) are listed in Table 2, as well as the properties of those compositions.

[0136] [Table 3]

[0137] As shown in Table 2, two of the comparative compositions (Comparative Example 1 and Comparative Example 4) contained imidazole (identified as Imidazole A and Imidazole B), but these imidazoles (Imidazole A and Imidazole B) were not encapsulated imidazoles and therefore were not encapsulated imidazoles with potential thermal activity within the meaning of this disclosure. Imidazole A is 2-phenylimidazole. Imidazole B is 2-ethyl-4-methyl-1H-imidazole-1-propanenitrile. Two of the comparative compositions (Comparative Example 2 and Comparative Example 3) did not contain any imidazole. The composition of Example 1 formed good solder interconnects and demonstrated no material entrapment in the thermocompression bonding process, and also demonstrated good high temperature properties of high Tg and low CTE compared to the comparative examples. The compositions of Comparative Examples 1, 2, and 4 were deemed unsuitable for the thermocompression bonding process. The composition of Comparative Example 3 formed good solder interconnects and no material entrapment during thermocompression, while the compositions of Comparative Examples 1-4 all exhibited subpar high temperature properties.

[0138] Thus, without being bound by theory, it is believed that compositions that include imidazoles with latent thermal activity, e.g., encapsulated imidazoles with latent thermal activity, provide characteristics that make the compositions more suitable for thermocompression bonding processes, including, but not limited to, DSC onset temperature, melt viscosity, and ΔT from DSC onset temperature to DSC peak temperature, while compositions that include imidazoles that do not have latent thermal activity and compositions that do not include imidazoles are less suitable for thermocompression bonding processes.

Claims

1. One or more resins selected from the group consisting of maleimide-containing resins, nadiimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenol-containing resins. One or more encapsulated imidazoles having latent thermal activity, One or more inorganic fillers, and One or more additives selected from the group consisting of adhesion promoters and film-forming agents, A composition comprising, After the composition forms a film, the film has the following physical properties: Tg > 200°C as measured by dynamic mechanical analysis (DMA), Storage modulus at 25°C < 6.5 GPa, Storage modulus at 250°C > 0.1 GPa, Coefficient of thermal expansion (CTE) < 250 ppm / °C, Differential scanning calorimetry (DSC) starting temperature of 120°C to 200°C, measured by DSC at a ramp rate of 10°C / min, and The minimum film melt viscosity measured in N2 was 10 Pa·s to 10,000 Pa·s using a DHR2 rheometer at a ramp rate of 10°C / min. A composition having the following characteristics.

2. After the composition forms a film, the film has the following physical properties: Tg > 230°C as measured by dynamic mechanical analysis (DMA), Storage modulus at 25°C < 5 GPa, Storage modulus at 230°C > 0.3 GPa, and Coefficient of thermal expansion (CTE) < 120 ppm / °C, The composition according to claim 1, having the following characteristics.

3. The maleimide-containing resin is 【Chemistry 1】 (In the formula, Each R is independently selected from the group consisting of H and substituted or unsubstituted alkyl groups; Each m is independently selected from the group consisting of 0, 1, 2, 3, or 4; n is 0, 1, 2, 3, 4, or 5. The compound represented by or 【Chemistry 2】 (wherein n is 0, 1, 2, 3, 4, or 5). The composition according to claim 1, as represented by [the specified formula].

4. The (meth)acrylic resin mentioned above 【Transformation 3】 (In the formula, n is 0, 1, 2, 3, 4, or 5) The composition according to claim 1, as represented by [the specified formula].

5. The epoxy resin, 【Chemistry 4】 (In the formula, n is 0, 1, 2, 3, 4, or 5, and m is 0, 1, 2, 3, 4, or 5) The composition according to claim 1, wherein the compound is represented by [the formula shown].

6. After the composition forms a film, the film has the following physical properties: The differential scanning calorimetry (DSC) start temperature measured by DSC at a ramp rate of 10°C / min was 120°C to 150°C, and Using a DHR2 rheometer at a ramp speed of 10°C / min, N ２ The lowest film melt viscosity measured inside was 300 Pa·s to 3,000 Pa·s. The composition according to claim 1 or 2, having the following characteristics.

7. The composition according to claim 1 or 2, wherein, after the composition forms a film, the ΔT from the DSC start temperature to the DSC peak temperature of the film is less than 20°C.

8. The composition according to claim 1 or 2, wherein, after the composition forms a film, the ΔT from the DSC start temperature to the DSC peak temperature of the film is less than 15°C.

9. The composition according to claim 1 or 2, wherein, after the composition forms a film, the ΔT from the DSC start temperature to the DSC peak temperature of the film is less than 10°C.

10. The composition according to claim 1 or 2, wherein, after the composition forms a film, the ΔT from the DSC start temperature to the DSC peak temperature of the film is less than 5°C.

11. A step of preparing the composition according to claim 1; A step of forming the aforementioned composition into a film; The process involves exposing the molded film to a high temperature to harden the film; A method for preparing a cured film, including [a specific component].

12. One or more resins selected from the group consisting of maleimide-containing resins, nadiimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenol-containing resins. One or more encapsulated imidazoles having latent thermal activity, One or more inorganic fillers, and One or more additives selected from the group consisting of adhesion promoters and film-forming agents, A step of preparing a composition containing; A step of forming the aforementioned composition into a film; The process involves exposing the molded film to a high temperature to harden the film; A method for preparing a cured film, including [a specific component].

13. The maleimide-containing resin is 【Transformation 5】 (In the formula, Each R is independently selected from the group consisting of H and substituted or unsubstituted alkyl groups; Each m is independently selected from the group consisting of 0, 1, 2, 3, or 4; n is 0, 1, 2, 3, 4, or 5. The compound represented by or 【Transformation 6】 (wherein n is 0, 1, 2, 3, 4, or 5). The method according to claim 11 or 12, wherein the compound is represented by the compound.

14. The (meth)acrylic resin mentioned above 【Transformation 7】 (wherein n is 0, 1, 2, 3, 4, or 5). The method according to claim 11 or 12, as represented by the following:

15. The epoxy resin, 【Transformation 8】 (In the formula, n is 0, 1, 2, 3, 4, or 5, and m is 0, 1, 2, 3, 4, or 5) The method according to claim 11 or 12, wherein the compound is represented by the compound.

16. A cured film prepared according to the method described in claim 11 or 12.

17. The aforementioned film has the following physical properties: Tg > 200°C as measured by dynamic mechanical analysis (DMA), Storage modulus at 25°C < 5.5 GPa, Storage modulus at 250°C > 0.1 GPa, and Coefficient of thermal expansion (CTE) < 250 ppm / °C, A film having the characteristics of a film prepared according to the method of claim 11.

18. The aforementioned film has the following physical properties: Tg > 230°C as measured by dynamic mechanical analysis (DMA), Storage modulus at 25°C < 5 GPa, Storage modulus at 230°C > 0.2 GPa, and Coefficient of thermal expansion (CTE) < 120 ppm / °C, A film having the characteristics of a film prepared according to the method of claim 11 or 12.

19. The film according to claim 16, wherein the film is an underfill film.

20. The film according to claim 19, wherein the film is a wafer-level underfill film (WAUF).

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