Reworkable compositions of oxirane(s) or thirane(s)-containing resin and curing agent

1. A method of sealing underfilling between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which said semiconductor device is electrically connected, or a semiconductor chip and a circuit board to which said semiconductor chip is electrically connected, the steps of which comprise:

(a) dispensing into the underfilling between the semiconductor device and the circuit board, or the semiconductor chip and the circuit board a composition comprising:

(i) from about 10 to about 70 weight precent of a curable resin component, based on the weight of the total composition, wherein from about 25 to about 75 weight percent is a compound having at least one linkage selected from the group consisting of oxiranes and thiiranes, substituted on at least three of the substitutable positions on the oxirane or thiirane carbons, respectively, with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interruption by one or more heteroatorns or halogens (I); and

(ii) a curing agent component selected from the group consisting of anhydride compounds, amine compounds, amide compounds, imidazole compounds, and combinations thereof, provided that the compound I does not include as its sole component an epoxy compound within any of the following formulae [II:

wherein each R is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, C 1-4 alkoxy, halogen, cyano and nitro, R 1 and R 2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, and propyl, provided that both R 1 and R 2 cannot be hydrogen, and R 3 is independently selected from the group consisting of propyl, and isopropyl, provided at least one of R 3a and R 3b , and at least one of R 3c and R 3d is independently selected from the group consisting of methyl, ethyl, propyl, and isopropyl, and m is 0 or 1]

wherein each R is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertbutyl, C 1-4 alkoxy, halogens, cyano and nitro, and phenyl, and R 3 and R 4 together form an epoxy group, and R 1 and R 2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, and phenyl, except that at least one of R 1 and R 2 is not hydrogen, and n is 0 and p is 0 and m is 0 or 1;

wherein R, R 1 , R 2 , R 3 , and R 4 are as defined above and m is 1 and p is 1 and n is 1 or p is 0 and m is 0 and n is 1, and the compounds are symmetrical;

wherein R is defined as above and the compounds are symmetrical; and

wherein R, R 1 and R 2 are defined as above and c and d are both 1 or c and d are both 0 and the compounds are symmetrical; and

(b) exposing the composition as so dispensed to conditions appropriate to cause the composition to form a reaction product.

2. The method according to claim 1 , wherein the curable resin component includes a compound having at least one oxirane linkage substituted on at least three of the substitutable positions on the oxirane carbons with an alkyl, alkenyl or aryl substituent having a carbon content of 1 to about twelve carbon atoms, with or without substitution or interuption by one or more heteroatoms or halogens.

3. The method according to claim 1 , wherein the compound having at least one oxirane linkage is a member selected from the group consisting of oxiranes of 2,10-dimethyl-6-methylene-4,8-bis(2-methyl-1-propenyl 2,4,7,9-undecatetraene, 4-[(4E or 4Z)-1,5-dimethyl-4-heptenylidene or octenylidene]-1-methyl-cyclohexene, 1,1′-[(1E or 1Z, 3E or 3Z)-5-(1,1-dimethyl 2-propenyl)-3-(3-methyl-2-butenyl)-1,3-pentadiene-1,5-diyl]bis-benzene, 4,6-dimethyl-[S or R-(E or Z, Z or E)]-2,5-octadiene, 2,6,10,14-tetramethyl-7-(3-methyl-4-pentenyl)-2,5,9,13-pentadecatetraene, 7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or 6Z, 10Z or 10E)-1,3,6,10-tridecatetraene, 3,4,8-trimethyl-1,4,7-nonatriene, 13-ethyl-9-methyl-1,9,12-pentadecatetraene, 1-methyl-4-(2-methyl-6-heptenylidene)-cyclohexene, 2,6,11-trimethyl-(E or Z)-2,5,10-dodecatriene, 2,6-dimethyl-(E or Z, E or Z)-2,6,9-tetradecatriene, 7-(3-methyl-2-butenyl-(E or Z)-6-dodecene, 6-(3-methyl-2-butenyl)-(E or Z)-6-dodecene, 2,4,6,6,8-pentamethyl-2,4,7-nonatriene, 3,7-dimethyl-11-(methyl)-(E or Z, E or Z)-1,3,6,10-dodecatetraene, 5-[3-methyl-1-(2-methyl-1-propenyl)-2-butenylidene]-1,3-cyclopentadiene, 4-[(4E or 4Z)-1,5-dimethyl-4-heptenylidene]-1-methyl-(4Z or 4E)-cyclohexene, 3,7,11-trimethyl-1,3,6,10-docosatetraene, 3,7,11,15-tetramethyl-1,3,6,10-hexadecatetraene, 9-ethyl-2,6-dimethyl-(E or Z, E or Z)-2,6,9-dodecatriene, 2-methyl-5-propyl-(E or Z)-2,5-nonadiene, 3,7,11-trimethyl-(Z or E, E or Z, E or Z)-1,3,6,10-dodecatetraene, 4,8,12-trimethyl-(Z or E, E or Z, E)-2,4,7,11-tridecatetraene, 1-methyl-4-(2-methyl-6-heptenylidene)-(E or Z)-cyclohexene, 3-ethyl-7,11-dimethyl-(E or Z, E or Z)-1,3,6,10-dodecatetraene, 2,6,6,9-tetramethyl-7-(2-methyl-1-propenyl)-2,4,8-decatriene, 2,7-dimethyl-4,5-bis(2-methyl-1-propenyl)-2,6-octadiene, 3,7-dimethyl-1,3,6-octatriene, 2-methyl-5-(1-methylethylidene)-cyclohexene, 2,6-dimethyl-5-(1-methylethylidene)-1,3-cyclohexadiene, 2,6-dimethyl-2,5-decadiene or octadiene, 7-ethyl-3,11-dimethyl-1,3,6,10-dodecatetraene, 2-methyl-(E or Z)-2,5-octadiene, 7-ethyl-3,11-dimethyl-(E or Z, E or Z)-1,3,6,10-dodecatetraene, 2,7,11-trimethyl-(E or Z)-2,5,10-dodecatriene, 6,10-dimethyl-(Z or E, Z or E)-2,6,9-undecatrien-4-yne, 2,6-dimethyl-(Z or E)-2,5-dodecadiene, 2,7-dimethyl-4,5-bis(2-methyl-1-propenyl)-2,4,6-octatriene, 2,3,6,7-tetramethyl-1,3,6-octatriene, 2-methyl-5-propyl-(Z or E)-2,5-dodecadiene, 2-methyl-5-(1-methylethyl)-(E or Z)-2,5-dodecadiene, 2-methyl-(Z or E)-2,5-dodecadiene, 2,4,4-trimethyl-(E or Z)-2,5-heptadiene, 2,6-dimethyl-2,5-octadiene, 3,4,7,11-tetramethyl-(E or Z, Z or E)-1,3,6,10-dodecatraene, 3,7,11-trimethyl-(E or Z, E or Z)-1,3,6,10-dodecatetraene, 4,8-dimethyl-1,4,7-nonatriene, 3,7,11,15-tetramethyl-1,3,6,10,14-hexadecapentaene, 2-methyl-(Z or E)-2,5-pentadecadiene, 2-methyl-5-(1-methylethylidene)-2-decene, 2,6-dimethyl-2,5,7-decatriene, 4,8-dimethyl-2,4,7-nonatriene, 15,19,23-trimethyl-15,18,22-heptatriacontatriene, 8-(2-methyl-1-propenyl)-6-tetradecene, 3,7,11-trimethyl-(E or Z)-1,3,6,10-dodecatetraene, 3,4-didehydro-2-(3-methyl-2-butenyl)-carotene, 7-ethyl-3,11-dimethyl-1,3,6,10-dodecatetraene, 1,3-dimethyl-4-propylidene cyclopentene, 2,7,11-trimethyl-(E or Z, E or Z)-1,3,6,10-dodecatetraene, 6,10-dimethyl-1,4,6,9-undecatetraene, 2-(1-methylethyl)-5-(1-methylethylidene)-1,3-cyclohexadiene, 2-ethyl-5-ethylidene-cyclohexadiene, 2-methyl-5-(1-methylethylidene)-1,3-cyclohexadiene, 3,7,10-trimethyl-(Z or E, E or Z)-1,3,6-undecatriene, 4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene, 1-methyl-4-(1-methylethylidene)-cyclohexene, 2,5-dimethyl-(Z or E)-2,5-heptadiene, 2-methyl-5-(1-methylethylidene)-1,3-cyclohexadiene, 2,6,10-trimethyl-(E or Z, Z or E)-2,6,9-tetradecatriene, 6-methyl-(Z or E, E or Z)-2,5-dodecadiene, 2,3,6-trimethyl-(E or Z, E or Z)-1,3,6-octatriene, tetrahydro-3,7,11-trimethyl-1,3,6,10-dodecatetraene, 3,4,7,11-tetramethyl-1,3,6,10-dodecatetraene, 3,4,7,11-tetramethyl-(Z or E, Z or E)-1,3,6,10-dodecatetraene, 2,6-dimethyl-4-methylene-2,5-heptadiene, 5-ethyl-2-methyl-2,5-heptadiene, 2,5-dimethyl-2,5-heptadiene or octadiene, 3,7,11-trimethyl-dodecatriene, 2,4,6,6,8-pentamethyl-(E or Z)-2,4,7-nonatriene, 3,7-diethyl-11-methyl-1,3,6,10-tridecatetraene, 7-ethyl-3,11-dimethyl-1,3,6,10-tridecatetraene, 2,6-dimethyl-(E or Z)-2,5-dodecadiene, 2,6,10-trimethyl (E or Z, E or Z)-2,6,9-tetradecatriene, 3,7,11,15-tetramethyl-(Z or E, E or Z, E or Z)-1,3,6,10,14-hexadecapentaene, 3,7,11,15-tetramethyl-(3E or 3Z, 6E or 6Z, 10E or 10Z)-1,3,6,10,14-hexadecapentaene, 1-ethenyl-4-(1-methylethylidene)-cyclohexene, 1-methyl-6-methylene-4-(1-methylethylidene)-cyclohexene, 3,7,11-trimethyl-1,3,6-dodecatriene, 4-(1,5-dimethylhexylidene)-1-methyl-cyclohexene, 7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or 6Z)-1,3,6,10-dodecatetraene, 1,3,3′,4,4′,16-hexadehydro-1,2-dihydro-2,2′-bis-3-carotene, 7-methyl-(Z or E, Z or E)-3,6-dodecadiene, 6-ethylidene-2,3,10-trimethyl-(E or Z, E or Z)-1,3,9-undecatriene, 2,3,6,7,10,11-hexamethyl-(E or Z, E or Z)-1,3,6,10-dodecatetraene, 2,3,6,7-tetramethyl-(E or Z)-1,3,6-octatriene, 2,7,11-trimethyl-1,3,6,11-dodecatetraene, 3,7,11,15,19,23,27,31,35-nonamethyl-1,3,6,10,14,18,22,26,30,34-hexatriacontadecaene, 2,6-dimethyl-9-propyl-2,6,9-tridecatriene, 3,6-dimethyl-(E or Z, E or Z)-1,3,6-octatriene, 3,7-diethyl-11-methyl-(3Z or 3E, 6E or 6Z) 1,3,6,10-tridecatetraene, 7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or 6Z)-1,3,6,10-tridecatetraene, 1-methyl-4-(5-methyl-4-hexenylidene)-(4E or 4Z)-cyclohexene, 2,6,10-trimethyl-(Z or E)-2,5,9-undecatriene, 2,6,7,7-tetramethyl-(Z or E)-2,5-octadiene, 2,6,10,11,11-pentamethyl-2,6,9-dodecatriene, 2,6,10-trimethyl-2,6,9-tetradecatriene, 2,6-dimethyl-(Z or E)-2,5-decadiene, 6,10-dimethyl-1,6,9-undecatrien-4-yne, 2,3,6-trimethyl-2,5-heptadiene, 2,4-dimethyl-(E or Z)-2,5-heptadiene, 2,7,11-trimethyl-(E or Z, E or Z)-1,3,6,11-dodecatetraene, 6-ethyl-3-methyl-2,5-decadiene, 2,6,10-trimethyl-(Z or E)-2,5-undecadiene, 3,7-dimethyl-3,6-octadien-1-yne, 2,7,10-trimethyl-1,6,9-undecatriene, 4,5-dimethyl-(E or Z, E or Z, E or Z)-3,5,8-undecatriene, 4,5-dimethyl-2,5,8-undecatriene, 1′-[4-methyl-2-(2-methyl-1-propenyl)-1,3-pentadienylidene]bis-benzene, 1, 4-1(1,5-dimethyl-4-hexenylidene)-1 methyl-(4E or 4Z)-cyclohexene, 2,6,11,15-tetramethyl-(Z or E)-2,6,9,14-hexadecatetraene, [3 methyl-1-(2-methyl-1-propenyl)-2-butenyl]-benzene, 2,6,11-trimethyl-(E or Z, E or Z)-2,6,9-dodecatriene, 2,6-dimethyl-(E or Z, E or Z)-2,6,9-dodecatriene, 2,3,6,7,10,11-hexamethyl-1,3,6,11-dodecatetraene, 19 methyl-1-(2-methyl-1-2,4,6,8,10,12,14,16,18-eicosanonaenylium, 17-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12,14,16-octadecaoctaenylium, 15-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12,14-hexadecaheptaenylium, 13-methyl-1-(2-methyl-1 propenyl)-2,4,6,8,10,12-tetradecahexaenylium, 11-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10-dodecapentaenylium, 9-methyl-1-(2-methyl-1-propenyl)-2,4,6,8-decatetraenylium, 7-methyl-1-(2-methyl-1-propenyl)-2,4,6-octatrienylium, 4,ethylidene-2,6-dimethyl-2,5-heptadiene, 3,7,11-trimethyl-(E or Z)-3,6,11-dodecatrien-1-yne, 3,7-dimethyl-(3E or 3Z)-3,6-octadien-1-yne, 3,7-dimethyl-(E or Z)-3,6-nonadien-1-yne, 3,6,7-trimethyl-(E or Z)-3,6-octadien-1 yne, 7-ethyl-3-methyl-(E or Z)-3,6-nonadien-1-yne, 3,7,11-trimethyl-(Z or E)-3,6,11-dodecatrien-1-yne, 2,3,6,7,10,11-hexamethyl-1,3,6,11-dodecatetraene, 2,6-dimethyl-2,5-heptadiene, 2-methyl-2,5-heptadiene, 3,6,10-trimethyl-2,5,7,10-dodecatetraene, 2,7,10-trimethyl-1,3,7,10-dodecatetraene, 3,6-dimethyl-1,3,6-octatriene, 12-(2,2-dimethyl-6-methylenecyclohexyl)-3,8,8-trimethyl-11-methylene-(E or Z)-(S)-1,3,6-dodecatriene, ocimene, 3,7,11-trimethyl-,(3Z or 3E, 6Z or 6E)-1,3,6,10-dodecatetraene, 2-methyl-4-methylene-2,5-heptadiene, 3,8,8,14,18-pentamethyl-11-methylene-(E or Z)-1,3,6,13,17-nonadecapentaene, 2,7-dimethyl-2,5-octadiene, 3,8,8,14,18-pentamethyl-11-methylene-(E or Z, E or Z, E or Z)-1,3,6,13,17-nonadecapentaene, 6,10-dimethyl-2,4,6,9-undecatetraene, 2-methyl-(Z or E)-2,5-heptadiene, 2-methyl-(E or Z)-2,5-heptadiene, 3,7-dimethyl-1,3,6-octatriene, 4-(1,5-dimethyl-4-hexenylidene)-1-methyl-(4Z or 4E)-cyclohexene, 2,6,10,14,19,22,27,31-octamethyl-2,6,10,14,16,18,22,26,30-dotriacontanonaene, 2,6-dimethyl-2,5-heptadiene, 4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene, 3,7-dimethyl-(3E or 3Z)-1,3,6-octatriene, 2,6,10,14,19,23,31-heptamethyl-2,5,10,14,16,18,22,26,29-dotriacontanonaene, 3,7,dimethyl-(3Z or 3E)-1,3,6-octatriene, 3-methyl-1-(2-methyl-1-propenyl-(E or Z)-2-pentenyl, 2,6-dimethyl-4-(2-methylpropenyl)-1,3,5-heptatriene, 2,6-dimethyl-4-methylene-2,5-heptadiene, 1-methyl-4-(1-methylethylidene)-cyclohexene, 3,7,11-trimethyl-(3E or 3Z, 6E or 6Z)-1,3,6,10-dodecatetraene, 4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene, isoprene, myrcene, dihydromyrene, linalool, terpinenes (α, β, and γ), limonene, terpinolene, menthadiene (p-3,8 or p-2,4), geraniol, nerol, geranylacetate, neryl acetate, nerolidol, farnesol, dehydronerolidol, α-bisabolol, valancene, nookatene, nootkatone, dimethyl-2,4,6-octratriene, β-phellandrences, piperitols (−, cis and +, trans), 1-methyl-1,4-cyclohexadiene, methyl cyclopentadiene dimer, ethylidene norbornene, dipentene, carvestrene, carvone (− or +), alloocimenes [4-trans-6-cis and 4-trans-6-trans], alloocimenols, ionomers, guaiazulene, lanosterol, squalene, lycopene, carotenes [β and γ], and combinations thereof.

4. The method according to claim 1 , wherein the compound having at least one oxirane linkage is a member selected from the group consisting of limonene diepoxide, gamma-terpinene diepoxide, and combinations thereof.

5. The method according to claim 1 , wherein the curing agent component is selected from the group consisting of anhydride components, amine compounds, amide compounds, imidazole compounds, and combinations thereof.

6. The method according to claim 1 , wherein the imidazole compounds of the curing agent component are selected from the group consisting of imidazole, isoimidazole, 2-methyl imidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, butylimidazole, 2-heptadecenyl-4-methylimidazole, 2-undecenylimidazole, 1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1 cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole, addition products of an imidazole and trimellitic acid, addition products of an imidazole and 2-n-heptadecyl-4-methylimidazole, phenylimidazole, benzylimidazole, 2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidazole, 2-styrylimidazole, 1-(dodecyl benzyl)-2-methylimidazole, 2-(2-hydroxyl-4-t butylphenyl)-4,5-diphenylimidazole, 2-(2-methoxyphenyl)-4,5-diphenylimidazole, 2-(3-hydroxyphenyl)-4,5-diphenylimidazole, 2-(p-dimethylaminophenyl)-4,5-diphenylimidazole, 2-(2-hydroxyphenyl)-4,5-diphenylimidazole, di(4,5-diphenyl-2-imidazole)-benzene-1,4, 2-napthyl-4,5-diphenylimidazole, 1-benzyl-2-methylimidazole, 2-p-methoxystyrylimidazole, and combinations thereof.

7. The method according to claim 1 , wherein the curing agent component is used in an amount of from about 3 to about 100 weight percent, based on the weight of the epoxy resin component.

8. The method according to claim 1 , wherein the curable resin component is present in an amount within the range of about 15 to 60 weight percent, based on the total weight of the composition; the curing agent component is present in an amount within the range of 3 to about 100 weight percent, based on the weight of the curable resin component; and further comprising an inorganic filler component in an amount up to about 70 weight percent, based on the total weight of the composition; and a flowability agent in an amount up to about 2 weight percent, based on the weight of the composition.