JPWO2015118836A1 - Resin composition containing polyimide precursor, method for producing cured film, and electronic component - Google Patents
Resin composition containing polyimide precursor, method for producing cured film, and electronic component Download PDFInfo
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- JPWO2015118836A1 JPWO2015118836A1 JP2015561208A JP2015561208A JPWO2015118836A1 JP WO2015118836 A1 JPWO2015118836 A1 JP WO2015118836A1 JP 2015561208 A JP2015561208 A JP 2015561208A JP 2015561208 A JP2015561208 A JP 2015561208A JP WO2015118836 A1 JPWO2015118836 A1 JP WO2015118836A1
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- resin composition
- group
- formula
- component
- cured film
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 68
- 229920001721 polyimide Polymers 0.000 title claims abstract description 32
- 239000004642 Polyimide Substances 0.000 title claims abstract description 24
- 239000002243 precursor Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 125000000962 organic group Chemical group 0.000 claims abstract description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 8
- -1 oxime ester compound Chemical class 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 97
- 239000002904 solvent Substances 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 17
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 16
- 230000008961 swelling Effects 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 125000003944 tolyl group Chemical group 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 0 C**(*)(*)**NC Chemical compound C**(*)(*)**NC 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 239000011162 core material Substances 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 2
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006358 imidation reaction Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical group CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 description 1
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-UHFFFAOYSA-N 0.000 description 1
- OJSPYCPPVCMEBS-UHFFFAOYSA-N 2,8-dimethyl-5,5-dioxodibenzothiophene-3,7-diamine Chemical compound C12=CC(C)=C(N)C=C2S(=O)(=O)C2=C1C=C(C)C(N)=C2 OJSPYCPPVCMEBS-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- GXDMUOPCQNLBCZ-UHFFFAOYSA-N 3-(3-triethoxysilylpropyl)oxolane-2,5-dione Chemical compound CCO[Si](OCC)(OCC)CCCC1CC(=O)OC1=O GXDMUOPCQNLBCZ-UHFFFAOYSA-N 0.000 description 1
- PMJIKKNFJBDSHO-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxy-3-methylpentane-1,5-diol Chemical compound NCCC[Si](OCC)(OCC)OC(C)(CCO)CCO PMJIKKNFJBDSHO-UHFFFAOYSA-N 0.000 description 1
- GIYJSTDNERTULV-UHFFFAOYSA-N 3-[4-[2-[4-(2,3-dicarboxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C(=C(C(O)=O)C=CC=3)C(O)=O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1C(O)=O GIYJSTDNERTULV-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
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Abstract
（ａ）下記式（１）で表される構造単位を有するポリイミド前駆体及び（ｂ）エチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物を含む樹脂組成物。但し、式（１）中、Ｒ１は４価の有機基であり、Ｒ２は２価の有機基である。Ｒ３及びＲ４は各々独立に水素原子、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、又は炭素炭素不飽和二重結合を有する１価の有機基である。(A) A resin composition comprising a polyimide precursor having a structural unit represented by the following formula (1) and (b) a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure. However, in Formula (1), R1 is a tetravalent organic group and R2 is a divalent organic group. R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond.
Description
本発明は、ポリイミド前駆体を含む樹脂組成物、それを用いた硬化膜の製造方法及び電子部品に関する。 The present invention relates to a resin composition containing a polyimide precursor, a method for producing a cured film using the resin composition, and an electronic component.
半導体集積回路の微細化に伴い、誘電率を低減するためのｌｏｗ−ｋ層と呼ばれる層間絶縁膜が必要とされている。ｌｏｗ−ｋ層は空孔構造を有するため、機械的強度が低下するという課題がある。この様な機械的強度の弱い層間絶縁膜を保護するために、ポリイミド樹脂から形成される硬化膜が用いられる。この硬化膜には、厚膜形成性（例えば５μｍ以上）や高弾性率化（例えば４ＧＰａ以上）といった特性が求められている。しかし、厚膜化及び高弾性率化に伴い、硬化後の応力が増大し、半導体ウエハの反りが大きくなって、搬送やウエハ固定の際に不具合が生じる場合があった。 With the miniaturization of semiconductor integrated circuits, an interlayer insulating film called a low-k layer for reducing the dielectric constant is required. Since the low-k layer has a pore structure, there is a problem that the mechanical strength is lowered. In order to protect such an interlayer insulating film having a low mechanical strength, a cured film formed of a polyimide resin is used. This cured film is required to have characteristics such as thick film formability (for example, 5 μm or more) and high elastic modulus (for example, 4 GPa or more). However, as the film thickness and the elastic modulus increase, the stress after curing increases and the warpage of the semiconductor wafer increases, which may cause problems during transportation and wafer fixing.
ポリイミド樹脂から形成される硬化膜を低応力化する方法として、例えば、酸成分に特定の官能基を有するフタル酸化合物を共重縮合させたポリアミドを用いる方法（例えば特許文献１）が挙げられる。しかしながら、近年は低温での硬化が求められており、前記ポリアミドを低温硬化させた場合には、充分な性能を有する硬化膜を得る点では改善の余地があった。 As a method for reducing the stress of a cured film formed from a polyimide resin, for example, there is a method using a polyamide obtained by copolycondensation of a phthalic acid compound having a specific functional group as an acid component (for example, Patent Document 1). However, in recent years, curing at a low temperature has been demanded, and when the polyamide is cured at a low temperature, there is room for improvement in terms of obtaining a cured film having sufficient performance.
また、低応力化するために、ｉ線透過率が高いフッ素を含有するポリイミド前駆体が検討されている。しかしながら、本発明者らの検討の結果、これらのポリイミド前駆体を含む樹脂組成物を加熱硬化後に得られる硬化膜は、レジストプロセス中に用いられる有機溶剤を吸収しやすく、膨潤してしまうことが判明した。ここでいう膨潤とは、ポリイミド硬化膜を一定温度（例えば７０℃）のＮ−メチルピロリドンに一定時間（例えば２０分間）浸漬したときに、硬化膜が溶媒を吸収し、体積が膨張する現象である。
本発明の目的は、３００℃以下の低温で硬化した場合であっても低応力及び低膨潤な硬化膜が得られる樹脂組成物を提供することである。In order to reduce the stress, a polyimide precursor containing fluorine having a high i-line transmittance has been studied. However, as a result of the study by the present inventors, a cured film obtained after heat curing a resin composition containing these polyimide precursors can easily absorb the organic solvent used during the resist process and swell. found. The swelling referred to here is a phenomenon in which when the polyimide cured film is immersed in N-methylpyrrolidone at a constant temperature (for example, 70 ° C.) for a certain time (for example, 20 minutes), the cured film absorbs the solvent and the volume expands. is there.
An object of the present invention is to provide a resin composition capable of obtaining a cured film having low stress and low swelling even when cured at a low temperature of 300 ° C. or lower.
本発明によれば、以下の樹脂組成物が提供される。
１．下記（ａ）成分及び（ｂ）成分を含む樹脂組成物。
（ａ）下記式（１）で表される構造単位を有するポリイミド前駆体、
（ｂ）エチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物
２．前記式（１）のＲ２が、下記式（２）で表わされる２価の有機基である１に記載の樹脂組成物。
４．前記光重合性化合物が、下記式（４）で表される構造を含む１〜３のいずれかに記載の樹脂組成物。
５．前記光重合性化合物が、下記式（５）で表される化合物である４に記載の樹脂組成物。
６．前記（ｂ）成分が前記（ａ）成分１００質量部に対して０．０１〜５０質量部含まれる１〜５のいずれかに記載の樹脂組成物。
７．（ｃ）成分として、活性光線照射によりラジカルを発生する化合物をさらに含む１〜６のいずれかに記載の樹脂組成物。
８．前記活性光線照射によりラジカルを発生する化合物が、オキシムエステル化合物である７に記載の樹脂組成物。
９．（ｅ）成分として、（ｂ）成分以外の光重合性化合物をさらに含む１〜８のいずれかに記載の樹脂組成物。
１０．前記光重合性化合物が、（メタ）アクリル化合物である９に記載の樹脂組成物。
１１．１〜１０のいずれかに記載の樹脂組成物を基板上に塗布し乾燥して塗膜を形成する工程と、前記塗膜を加熱処理する工程とを含む、硬化膜の製造方法。
１２．１〜１０のいずれかに記載の樹脂組成物を基板上に塗布し乾燥して塗膜を形成する工程と、前記塗膜に活性光線を照射後、現像してパターン樹脂膜を得る工程と、前記パターン樹脂膜を加熱処理する工程とを含む、パターン硬化膜の製造方法。
１３．１１に記載の硬化膜の製造方法から得られる硬化膜。
１４．１２に記載のパターン硬化膜の製造方法から得られるパターン硬化膜。
１５．１３に記載の硬化膜又は１４に記載のパターン硬化膜をを有する電子部品。According to the present invention, the following resin composition is provided.
1. The resin composition containing the following (a) component and (b) component.
(A) a polyimide precursor having a structural unit represented by the following formula (1),
(B) a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure; 2. The resin composition according to 1, wherein R 2 in the formula (1) is a divalent organic group represented by the following formula (2).
4). The resin composition in any one of 1-3 in which the said photopolymerizable compound contains the structure represented by following formula (4).
5). 5. The resin composition according to 4, wherein the photopolymerizable compound is a compound represented by the following formula (5).
6). The resin composition according to any one of 1 to 5, wherein the component (b) is contained in an amount of 0.01 to 50 parts by mass with respect to 100 parts by mass of the component (a).
7). (C) The resin composition in any one of 1-6 which further contains the compound which generate | occur | produces a radical by irradiation with actinic light as a component.
8). 8. The resin composition according to 7, wherein the compound that generates radicals upon irradiation with actinic rays is an oxime ester compound.
9. (E) The resin composition in any one of 1-8 which further contains photopolymerizable compounds other than (b) component as a component.
10. 10. The resin composition according to 9, wherein the photopolymerizable compound is a (meth) acrylic compound.
The manufacturing method of a cured film including the process of apply | coating the resin composition in any one of 11.1-10 on a board | substrate, drying and forming a coating film, and the process of heat-processing the said coating film.
A step of applying the resin composition according to any one of 12.1 to 10 on a substrate and drying to form a coating film, and a step of irradiating the coating film with actinic rays and developing to obtain a patterned resin film And a step of heat-treating the patterned resin film.
A cured film obtained from the method for producing a cured film according to 13.11.
The pattern cured film obtained from the manufacturing method of the pattern cured film as described in 14.12.
15. An electronic component having the cured film according to 15.13 or the pattern cured film according to 14.
本発明によれば、３００℃以下の低温で硬化した場合であっても低応力及び低膨潤な硬化膜が得られる樹脂組成物が提供できる。 ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where it hardens | cures at the low temperature of 300 degrees C or less, the resin composition from which the cured film with a low stress and a low swelling is obtained can be provided.
以下に、本発明にかかる樹脂組成物及び該樹脂組成物を用いた硬化膜の製造方法について説明する。尚、この実施の形態により本発明が限定されるものではない。 Below, the resin composition concerning this invention and the manufacturing method of the cured film using this resin composition are demonstrated. In addition, this invention is not limited by this embodiment.
本発明の樹脂組成物は、下記（ａ）成分及び（ｂ）成分を含む。
［（ａ）成分］
下記式（１）で表される構造単位を有するポリイミド前駆体
［（ｂ）成分］
エチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物The resin composition of this invention contains the following (a) component and (b) component.
[(A) component]
Polyimide precursor having a structural unit represented by the following formula (1)
[Component (b)]
Photopolymerizable compound having ethylenically unsaturated group and isocyanuric ring structure
従来は、３７０℃程度の高温でポリイミド前駆体の加熱硬化が行われていたが、本発明の樹脂組成物は、（ａ）成分と（ｂ）成分の両方を含むことで、３００℃以下の低温で硬化した場合であっても、応力が低くかつ膨潤が発生しにくい硬化膜が得られる。（ａ）成分を用いなかった場合、例えばポリベンゾオキサゾール前駆体を用いた場合は、（ｂ）成分を併用しても、応力及び膨潤に対する効果が低い。
以下、本発明の樹脂組成物の各成分について説明する。Conventionally, the polyimide precursor was heat-cured at a high temperature of about 370 ° C., but the resin composition of the present invention contains both the component (a) and the component (b), so that the temperature is 300 ° C. or less. Even when cured at a low temperature, a cured film having low stress and less likely to swell can be obtained. When the component (a) is not used, for example, when a polybenzoxazole precursor is used, the effect on stress and swelling is low even when the component (b) is used in combination.
Hereinafter, each component of the resin composition of this invention is demonstrated.
（ａ）成分：下記式（１）で表される構造単位を有するポリイミド前駆体
式（１）中のＲ１は、原料として用いられるテトラカルボン酸又はその二無水物に由来する構造である。硬化膜の応力、ｉ線透過率の観点からは、Ｒ１は、下記式（２ａ）〜（２ｅ）で表される基のいずれかであることが好ましい。
式（２ｄ）のＸ及びＹの「結合するベンゼン環と共役しない２価の基」は、例えば、−Ｏ−、−Ｓ−、又は下記式で表わされる２価の基である。
Ｒ１３は、各々独立に水素原子、又は、フッ素原子等のハロゲン原子である。）
これらの中でも、Ｒ１はピロメリット酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物又は３，３’，４，４’−ビフェニルテトラカルボン酸二無水物に由来する構造がより好ましい。これらは単独又は２種類以上を組み合わせて用いることができる。The “divalent group that is not conjugated with the benzene ring to be bonded” of X and Y in the formula (2d) is, for example, —O—, —S—, or a divalent group represented by the following formula.
R 13 is each independently a hydrogen atom or a halogen atom such as a fluorine atom. )
Among these, R 1 is derived from pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. A structure is more preferable. These can be used alone or in combination of two or more.
硬化膜の応力、ｉ線透過率を低下させない範囲において、Ｒ１の原料は３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、１，２，５，６−ナフタレンテトラカルボン酸二無水物、２，３，５，６−ピリジンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、３，４，９，１０−ペリレンテトラカルボン酸二無水物、ｍ−ターフェニル−３，３’，４，４’−テトラカルボン酸二無水物、ｐ−ターフェニル−３，３’，４，４’−テトラカルボン酸二無水物、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、２，２−ビス｛４’−（２，３−ジカルボキシフェノキシ）フェニル｝プロパン二無水物、２，２−ビス｛４’−（３，４−ジカルボキシフェノキシ）フェニル｝プロパン二無水物、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス｛４’−（２，３−ジカルボキシフェノキシ）フェニル｝プロパン二無水物、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス｛４’−（３，４−ジカルボキシフェノキシ）フェニル｝プロパン二無水物、４，４’−オキシジフタル酸二無水物、４，４’−スルホニルジフタル酸二無水物等と組み合わせて用いてもよい。As long as the stress of the cured film and the i-line transmittance are not lowered, the raw material of R 1 is 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride M-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, p-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,1, 1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis {4 ′-(2,3-dicarboxyphenoxy) ) Phenyl} propane dianhydride, 2,2-bis {4 ′-(3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 1,1,1,3,3,3-hexafluoro-2, 2-bis {4 '-(2,3-dicarboxyphenoxy) phenyl} propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis {4'-(3 4-Dicarboxyphenoxy) phenyl} propane dianhydride, 4,4′-oxydiphthalic dianhydride, 4,4′-sulfonyldiphthalic dianhydride and the like may be used.
式（１）中のＲ２は原料として用いるジアミンに由来する構造である。（ａ）成分において、式（１）中のＲ２が、下記式（２）で表わされる２価の有機基であることが好ましい。
Ｒ５〜Ｒ１２の１価の有機基としては、例えば炭素数１〜１０（好ましくは炭素数１〜６）のアルキル基、炭素数１〜１０（好ましくは炭素数１〜６）のフルオロアルキル基が挙げられる。Examples of the monovalent organic group represented by R 5 to R 12 include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluoroalkyl having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Groups.
（ａ）成分において、式（１）中のＲ２が、下記式（３）で表わされる２価の有機基であることがより好ましい。低温硬化時における膨潤現象は、ｉ線透過率が高いフッ素を含有するポリイミド前駆体を用いた際に生じやすい傾向がある。
（ａ）成分中、式（１）中のＲ２が式（３）で表される構造単位である割合は、１〜１００ｍｏｌ％であることが好ましく、１０〜１００ｍｏｌ％であることがより好ましく、３０〜１００ｍｏｌ％であることがさらに好ましい。In the component (a), the ratio in which R 2 in the formula (1) is a structural unit represented by the formula (3) is preferably 1 to 100 mol%, and more preferably 10 to 100 mol%. More preferably, it is 30-100 mol%.
式（２）又は（３）で表される構造としては、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、２，２’−ビス（フルオロ）−４，４’−ジアミノビフェニル、４，４’−ジアミノオクタフルオロビフェニルが挙げられる。これらは単独で又は２種類以上を組み合わせて用いることができる。 Examples of the structure represented by the formula (2) or (3) include 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′-bis (fluoro) -4,4 ′. -Diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.
また、式（２）、（３）以外の構造を与えるジアミン化合物を用いることもできる。例えば、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−キシリレンジアミン、ｍ−キシリレンジアミン、１，５−ジアミノナフタレン、ベンジジン、４，４’−（又は３，４’−、３，３’−、２，４’−、２，２’−）ジアミノジフェニルエーテル、４，４’−（又は３，４’−、３，３’−、２，４’−、２，２’−）ジアミノジフェニルスルフォン、４，４’−（又は３，４’−、３，３’−、２，４’−、２，２’−）ジアミノジフェニルスルフィド、ｏ−トリジン、ｏ−トリジンスルホン、４，４’−メチレン−ビス（２，６−ジエチルアニリン）、４，４’−メチレン−ビス（２，６−ジイソプロピルアニリン）、２，４−ジアミノメシチレン、１，５−ジアミノナフタレン、４，４’−ベンゾフェノンジアミン、ビス−｛４−（４’−アミノフェノキシ）フェニル｝スルホン、２，２−ビス｛４−（４’−アミノフェノキシ）フェニル｝プロパン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、３，３’，５，５’−テトラメチル−４，４’−ジアミノジフェニルメタン、ビス｛４−（３’−アミノフェノキシ）フェニル｝スルホン、２，２−ビス（４−アミノフェニル）プロパン、ジアミノポリシロキサン等が挙げられる。これらは単独で又は２種類以上を組み合わせて用いることができる。 Moreover, the diamine compound which gives structures other than Formula (2) and (3) can also be used. For example, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4 ′-(or 3,4′-, 3,3 ′ -, 2,4'-, 2,2 '-) diaminodiphenyl ether, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenyl Sulfone, 4,4 ′-(or 3,4′-, 3,3′-, 2,4′-, 2,2 ′-) diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4 ′ -Methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenone Diamine, bi -{4- (4'-aminophenoxy) phenyl} sulfone, 2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3 , 3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, bis {4- (3′-aminophenoxy) phenyl} sulfone, 2,2-bis (4-aminophenyl) propane, diaminopoly Examples thereof include siloxane. These can be used alone or in combination of two or more.
式（１）中のＲ３及びＲ４は、各々独立に水素原子、炭素数１〜２０（好ましくは炭素数１〜１０、より好ましくは炭素数１〜６）のアルキル基、炭素数３〜２０（好ましくは炭素数５〜１５、より好ましくは炭素数６〜１２）のシクロアルキル基、又は炭素炭素不飽和二重結合を有する１価の有機基である。R 3 and R 4 in Formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), and 3 to 3 carbon atoms. A cycloalkyl group having 20 (preferably 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms), or a monovalent organic group having a carbon-carbon unsaturated double bond.
炭素数１〜２０のアルキル基としてはメチル基、エチル基、ｎ−プロピル基、２−プロピル基、ｎ−ブチル基等が挙げられる。炭素数３〜２０のシクロアルキル基としてはシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、アダマンチル基等が挙げられる。
炭素炭素不飽和二重結合を有する１価の有機基としては、例えば、（メタ）アクリル基を有する有機基が挙げられる。具体的には、アルキル基の炭素数が１〜１０の（メタ）アクリロキシアルキル基が挙げられる。なお、「（メタ）アクリル」とは「メタクリル」又は「アクリル」を表し、「（メタ）アクリロキシ」とは「メタクリロキシ」又は「アクリロキシ」を表し、「（メタ）アクリレート」は「メタクリレート」又は「アクリレート」を表す。
アルキル基の炭素数が１〜１０の（メタ）アクリロキシアルキル基としては、（メタ）アクリロキシエチル基、（メタ）アクリロキシプロピル基、（メタ）アクリロキシブチル基等が挙げられる。Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n-butyl group. Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
Examples of the monovalent organic group having a carbon-carbon unsaturated double bond include an organic group having a (meth) acryl group. Specific examples include (meth) acryloxyalkyl groups having 1 to 10 carbon atoms in the alkyl group. “(Meth) acryl” means “methacryl” or “acryl”, “(meth) acryloxy” means “methacryloxy” or “acryloxy”, and “(meth) acrylate” means “methacrylate” or “ Acrylate ".
Examples of the (meth) acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group include (meth) acryloxyethyl group, (meth) acryloxypropyl group, (meth) acryloxybutyl group and the like.
Ｒ３及びＲ４の少なくとも一方が、炭素炭素不飽和二重結合を有する１価の有機基の場合は、活性光線照射によってラジカルを発生する化合物と組み合わせることで、ラジカル重合による分子鎖間の架橋が可能となる感光性樹脂組成物となる。When at least one of R 3 and R 4 is a monovalent organic group having a carbon-carbon unsaturated double bond, it is combined with a compound that generates radicals upon irradiation with actinic rays, thereby crosslinking between molecular chains by radical polymerization. It becomes the photosensitive resin composition which becomes possible.
本発明の（ａ）成分は、テトラカルボン酸二無水物とジアミンを付加重合させて合成することができる。また、式（５）で表されるテトラカルボン酸二無水物をジエステル誘導体にした後、式（６）で表される酸塩化物に変換し、式（７）で表されるジアミンと反応させることによって合成することができる。合成方法は公知の手法から選択できる。
（ａ）成分であるポリイミド前駆体の分子量は、ポリスチレン換算での重量平均分子量が１００００〜１０００００であることが好ましく、１５０００〜１０００００であることがより好ましく、２００００〜８５０００であることがさらに好ましい。重量平均分子量が１００００より大きいと、硬化後の応力を充分に低下することができる。また、１０００００より小さいと、溶剤への溶解性を向上よりでき、溶液の粘度が減少して取り扱い性が向上する。尚、重量平均分子量は、ゲルパーミエーションクロマトグラフィー法によって測定することができ、標準ポリスチレン検量線を用いて換算することによって求めることができる。 As for the molecular weight of the polyimide precursor as component (a), the weight average molecular weight in terms of polystyrene is preferably 10,000 to 100,000, more preferably 15,000 to 100,000, and still more preferably 20,000 to 85,000. When the weight average molecular weight is greater than 10,000, the stress after curing can be sufficiently reduced. On the other hand, if it is less than 100,000, the solubility in the solvent can be improved, the viscosity of the solution is reduced, and the handleability is improved. In addition, a weight average molecular weight can be measured by the gel permeation chromatography method, and can be calculated | required by converting using a standard polystyrene calibration curve.
（ａ）成分を合成する際のテトラカルボン酸二無水物とジアミンのモル比は通常１．０であるが、分子量や末端残基を制御する目的で、０．７〜１．３の範囲のモル比であってもよい。モル比が０．７以下もしくは１．３以上の場合、得られるポリイミド前駆体の分子量が小さくなり、硬化後の低応力性が充分に発現しない恐れがある。 The molar ratio of tetracarboxylic dianhydride and diamine when synthesizing the component (a) is usually 1.0, but in the range of 0.7 to 1.3 for the purpose of controlling the molecular weight and terminal residue. It may be a molar ratio. When the molar ratio is 0.7 or less or 1.3 or more, the molecular weight of the obtained polyimide precursor becomes small, and the low stress property after curing may not be sufficiently exhibited.
本発明の（ａ）成分であるポリイミド前駆体を加熱処理してイミド化を進行させてポリイミドに変換する加熱温度としては、８０〜３００℃が好ましく、１００〜３００℃がより好ましく、２００〜３００℃であることがさらに好ましい。８０℃未満ではイミド化が充分進行せず、耐熱性が低下する恐れがあり、３００℃より高い温度で行うと、半導体素子へダメージを与えてしまう恐れがある。 As heating temperature which heat-processes the polyimide precursor which is (a) component of this invention, advances imidation, and converts it into a polyimide, 80-300 degreeC is preferable, 100-300 degreeC is more preferable, 200-300 More preferably, the temperature is C. If it is less than 80 ° C., imidization does not proceed sufficiently and the heat resistance may be lowered, and if it is performed at a temperature higher than 300 ° C., the semiconductor element may be damaged.
式（１）で表されるポリイミド前駆体を基材に塗布し、加熱硬化して得られる硬化膜の残留応力は、硬化膜の膜厚が１０μｍの場合において、３０ＭＰａ以下であることが好ましく、２７ＭＰａ以下であることがより好ましく、２５ＭＰａ以下であることがさらに好ましい。残留応力が３０ＭＰａ以下であれば、硬化後の膜厚が１０μｍとなるように膜を形成した場合に、ウエハの反りをより充分抑制することができ、ウエハの搬送や吸着固定において生じる不具合をより抑制することができる。 The residual stress of the cured film obtained by applying the polyimide precursor represented by the formula (1) to the substrate and heat-curing is preferably 30 MPa or less when the thickness of the cured film is 10 μm. The pressure is more preferably 27 MPa or less, and further preferably 25 MPa or less. If the residual stress is 30 MPa or less, when the film is formed so that the film thickness after curing is 10 μm, the warpage of the wafer can be more sufficiently suppressed, and the problems caused in the conveyance and suction fixation of the wafer can be further reduced. Can be suppressed.
尚、残留応力は薄膜ストレス測定装置ＦＬＸ−２３２０（ＫＬＡ Ｔｅｎｃｏｒ社製）を用いて、ウエハの反り量を測定後、応力に換算する方法により測定することができる。 The residual stress can be measured by a method of converting the amount of warpage of the wafer into a stress after measuring the amount of warpage of the wafer using a thin film stress measuring apparatus FLX-2320 (manufactured by KLA Tencor).
本発明において得られる硬化膜を、硬化後の膜厚が１０μｍとなるように形成するためには、上述の樹脂組成物を基板上に塗布し乾燥して塗膜を形成する工程後に、塗膜の厚さが２０μｍ程度である必要がある。よって、活性光線照射によってラジカルを発生する化合物と組み合わせて感光性樹脂組成物とする場合には、樹脂組成物のｉ線透過率が高いほど好ましい。 In order to form the cured film obtained in the present invention so that the film thickness after curing is 10 μm, the above-mentioned resin composition is applied onto a substrate and dried to form a coated film, Needs to be about 20 μm thick. Therefore, when combining with the compound which generate | occur | produces a radical by actinic-light irradiation and it is set as the photosensitive resin composition, it is so preferable that i line | wire transmittance of a resin composition is high.
具体的には、膜厚２０μｍにおいて、ｉ線透過率が５％以上であることが好ましく、８％以上であることがより好ましく、１５％以上であることがさらに好ましい。５％未満であると、ｉ線が深部まで到達せず、ラジカルが充分に発生しないために、現像時に膜の基板側から樹脂が染み出てくる等、感光特性が低下する恐れがある。 Specifically, when the film thickness is 20 μm, the i-line transmittance is preferably 5% or more, more preferably 8% or more, and further preferably 15% or more. If it is less than 5%, the i-line does not reach the deep part, and radicals are not generated sufficiently. Therefore, there is a possibility that the photosensitive characteristics may be deteriorated, for example, the resin oozes out from the substrate side of the film during development.
尚、ｉ線透過率はＵ−３３１０ｓｐｃｔｒｏｐｈｏｔｏｍｅｔｅｒ（ＨＩＴＡＣＨＩ社製）を用いて、透過ＵＶスペクトルから測定することができる。 The i-line transmittance can be measured from a transmitted UV spectrum using U-3310 spcphotometer (manufactured by HITACHI).
（ｂ）成分：エチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物
本発明の樹脂組成物は、（ｂ）成分としてエチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物を含む。前記光重合性化合物は架橋剤として機能し、硬化後も膜中に残存することで、ポリイミド硬化膜中に架橋構造を形成し、膨潤を抑制することができると考えられる。また、光重合性化合物は、ポリイミド硬化膜の配向性を向上する機能を有し、硬化後の残膜率を向上することもできる。
尚、ポリイミド硬化膜の膨潤を抑制する添加剤としてアルミキレート化合物があるが、例えば３００℃以下の低温硬化においては、アルミキレート化合物の添加では充分な効果が得られない。上記（ｂ）成分を用いることにより、３００℃以下の低温硬化であっても充分な膨潤抑制効果が得られる。(B) Component: Photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure The resin composition of the present invention includes a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure as the component (b). . It is considered that the photopolymerizable compound functions as a crosslinking agent and remains in the film after curing, thereby forming a crosslinked structure in the cured polyimide film and suppressing swelling. Moreover, a photopolymerizable compound has a function which improves the orientation of a polyimide cured film, and can also improve the residual film rate after hardening.
In addition, although there exists an aluminum chelate compound as an additive which suppresses the swelling of a polyimide cured film, for example, in a low temperature curing of 300 ° C. or less, a sufficient effect cannot be obtained by adding an aluminum chelate compound. By using the component (b), a sufficient swelling suppressing effect can be obtained even at low temperature curing of 300 ° C. or lower.
上記光重合性化合物としては、トリアリルイソシアヌレート、トリアリルイソシアヌレートプレポリマー、及び下記式（４）で表される構造を有する化合物が好ましい。
式（４）で表される構造を有する化合物は、好ましくは下記式（５）で表される化合物である。
式（４）で表される構造を有する化合物として、下記式（６）で表される化合物も使用できる。
式（５）及び（６）の１価の有機基としては、炭素数１〜１５のアルキル基、グリシジル基、ビニル基等が挙げられる。炭素数１〜１５のアルキル基は、例えば２，３‐ジブロモプロピル基のようにハロゲン原子を有していてもよい。 Examples of the monovalent organic group of the formulas (5) and (6) include an alkyl group having 1 to 15 carbon atoms, a glycidyl group, and a vinyl group. The alkyl group having 1 to 15 carbon atoms may have a halogen atom such as a 2,3-dibromopropyl group.
式（４）及び（９）のＸ及びＹのアルキレン基の炭素数としては特に制限はないが、炭素数２〜７のアルキレン基であることが好ましく、炭素数２〜４のアルキレン基であることがより好ましく、エチレン基又はプロピレン基であることがさらに好ましい。 Although there is no restriction | limiting in particular as carbon number of the alkylene group of X and Y of Formula (4) and (9), It is preferable that it is a C2-C7 alkylene group, and it is a C2-C4 alkylene group. More preferred is an ethylene group or a propylene group.
式（４）及び式（９）のｎは、１〜２５の整数であり、１〜２０の整数であることが好ましく１〜１５の整数がより好ましい。
式（９）中のｍは、１〜１４の整数であり、１〜６の整数であることが好ましく６の整数であることがより好ましい。N of Formula (4) and Formula (9) is an integer of 1-25, it is preferable that it is an integer of 1-20, and the integer of 1-15 is more preferable.
M in the formula (9) is an integer of 1 to 14, preferably an integer of 1 to 6, and more preferably an integer of 6.
（ｂ）成分である光重合性化合物の具体例としては下記式（１０）で表される化合物が挙げられ、前記化合物は、Ａ−９３００（新中村化学工業株式会社製）として商業的に入手可能である。
本発明の樹脂組成物の（ｂ）成分の含有量は、膨潤抑制性及び膜物性の観点から、（ａ）成分１００重量部に対して１〜５０質量部が好ましく、１〜３０質量部がより好ましく、５〜２０質量部がさらに好ましい。
（ｂ）成分の含有量を（ａ）成分１００重量部に対して１質量部以上とすることにより硬化膜の有機溶剤による膨潤を抑制することができ、（ａ）成分１００重量部に対して５０質量部以下とすることにより硬化膜の伸びの低下を抑えることができる。The content of the component (b) of the resin composition of the present invention is preferably 1 to 50 parts by weight, and 1 to 30 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoint of swelling suppression and film properties. More preferred is 5 to 20 parts by mass.
(B) By making content of a component into 1 mass part or more with respect to 100 weight part of (a) component, the swelling by the organic solvent of a cured film can be suppressed, and with respect to 100 weight part of (a) component By making it 50 parts by mass or less, it is possible to suppress a decrease in elongation of the cured film.
（ｃ）成分：活性光線によりラジカルを発生する化合物
本発明の樹脂組成物は、（ｃ）成分として活性光線によりラジカルを発生する化合物を含有することが好ましい。
（ａ）成分のポリイミド前駆体の式（１）中のＲ３及び又はＲ４の少なくとも一部が、炭素炭素不飽和二重結合を有する１価の有機基である場合に、樹脂組成物が（ｃ）成分を含むことによって、本発明の樹脂組成物を感光性樹脂組成物とすることができる。Component (c): Compound that generates radicals by actinic rays The resin composition of the present invention preferably contains a compound that generates radicals by actinic rays as component (c).
When at least part of R 3 and / or R 4 in the formula (1) of the component (a) polyimide precursor is a monovalent organic group having a carbon-carbon unsaturated double bond, the resin composition is (C) By containing a component, the resin composition of this invention can be made into the photosensitive resin composition.
（ｃ）成分としては、例えば、後述するオキシムエステル化合物、ベンゾフェノン、Ｎ，Ｎ’−テトラメチル−４，４’−ジアミノベンゾフェノン（ミヒラーケトン）等のＮ，Ｎ’−テトラアルキル−４，４’−ジアミノベンゾフェノン；
２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパノン−１等の芳香族ケトン；
アルキルアントラキノン等の芳香環と縮環したキノン類；ベンゾインアルキルエーテル等のベンゾインエーテル化合物、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物；ベンジルジメチルケタール等のベンジル誘導体が挙げられる。これらは１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
これらの中でも、感度に優れ、良好なパターンを与えるため、オキシムエステル化合物が好ましい。Examples of the component (c) include N, N′-tetraalkyl-4,4′-, such as an oxime ester compound, benzophenone, and N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone) described later. Diaminobenzophenone;
Aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1;
Examples include quinones fused with an aromatic ring such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; and benzyl derivatives such as benzyldimethyl ketal. These may be used individually by 1 type and may be used in combination of 2 or more type.
Among these, an oxime ester compound is preferable because it is excellent in sensitivity and gives a good pattern.
オキシムエステル化合物は、下記式（９）で表される化合物、下記式（１０）で表される化合物又は下記式（１１）で表される化合物であることが好ましい。 The oxime ester compound is preferably a compound represented by the following formula (9), a compound represented by the following formula (10), or a compound represented by the following formula (11).
Ｒ２は、Ｈ、ＯＨ、ＣＯＯＨ、Ｏ（ＣＨ２）ＯＨ、Ｏ（ＣＨ２）２ＯＨ、ＣＯＯ（ＣＨ２）ＯＨ又はＣＯＯ（ＣＨ２）２ＯＨを示し、Ｈ、Ｏ（ＣＨ２）ＯＨ、Ｏ（ＣＨ２）２ＯＨ、ＣＯＯ（ＣＨ２）ＯＨ又はＣＯＯ（ＣＨ２）２ＯＨであることが好ましく、Ｈ、Ｏ（ＣＨ２）２ＯＨ又はＣＯＯ（ＣＨ２）２ＯＨであることがより好ましい。）
R 2 represents H, OH, COOH, O (CH 2 ) OH, O (CH 2 ) 2 OH, COO (CH 2 ) OH or COO (CH 2 ) 2 OH, and H, O (CH 2 ) OH O (CH 2 ) 2 OH, COO (CH 2 ) OH or COO (CH 2 ) 2 OH is preferred, and H, O (CH 2 ) 2 OH or COO (CH 2 ) 2 OH is preferred. More preferred. )
Ｒ４は、ＮＯ２又はＡｒＣＯ（ここで、Ａｒは置換もしくは無置換のアリール基を示す。）を示し、Ａｒとしては、トリル基が好ましい。
Ｒ５及びＲ６は、それぞれ炭素数１〜１２のアルキル基、フェニル基、又はトリル基を示し、メチル基、フェニル基又はトリル基であることが好ましい。）
R 4 represents NO 2 or ArCO (where Ar represents a substituted or unsubstituted aryl group), and Ar is preferably a tolyl group.
R 5 and R 6 each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and is preferably a methyl group, a phenyl group, or a tolyl group. )
Ｒ８はアセタール結合を有する有機基であり、後述する式（１１−１）に示す化合物が有するＲ８に対応する置換基であることが好ましい。また、Ｒ８が置換してるベンゼン環は、さらに置換基を有してもよい。
Ｒ９及びＲ１０は、それぞれ炭素数１〜１２のアルキル基、フェニル基又はトリル基を示し、メチル基、フェニル基又はトリル基であることが好ましく、メチル基であることがより好ましい。）
R 8 is an organic group having an acetal bond, and is preferably a substituent corresponding to R 8 included in the compound represented by formula (11-1) described later. In addition, the benzene ring substituted by R 8 may further have a substituent.
R 9 and R 10 each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, preferably a methyl group, a phenyl group, or a tolyl group, and more preferably a methyl group. )
上記式（９）で表される化合物としては、例えば、下記式（９−１）で表される化合物及び下記式（９−２）で表される化合物が挙げられる。これらのうち、下記式（９−１）で表される化合物はＩＲＧＡＣＵＲＥ ＯＸＥ−０１（ＢＡＳＦ株式会社製、商品名）として入手可能である。
上記式（１０）で表される化合物としては、例えば、下記式（１０−１）で表される化合物が挙げられる。この化合物は、ＤＦＩ−０９１（ダイトーケミックス株式会社製、商品名）として入手可能である。
上記式（１１）で表される化合物としては、例えば、下記式（１１−１）で表される化合物が挙げられる。アデカオプトマーＮ−１９１９（株式会社ＡＤＥＫＡ製、商品名）として入手可能である。
その他のオキシムエステル化合物としては、下記化合物を用いることが好ましい。
また、（ｃ）成分として、以下の化合物を用いることもできる。
（ｃ）成分を含有する場合の含有量としては、（ａ）成分１００質量部に対して、０．０１〜３０質量部であることが好ましく、０．０５〜１５質量部であることがより好ましく、０．１〜１０質量部であることがさらに好ましい。配合量が０．０１質量部以上であれば、露光部の架橋が充分し、より感光特性が良好となり、３０質量部以下であることより硬化膜の耐熱性が向上する傾向がある。 (C) As content in the case of containing a component, it is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of (a) component, and it is more preferable that it is 0.05-15 mass parts. Preferably, it is 0.1-10 mass parts. If the blending amount is 0.01 parts by mass or more, the exposed part is sufficiently cross-linked, the photosensitivity becomes more favorable, and the heat resistance of the cured film tends to be improved by being 30 parts by mass or less.
（ｄ）成分：溶剤
本発明の樹脂組成物は、（ｄ）成分として溶剤を含んでもよい。
（ｄ）成分である溶剤としては、ポリイミド前駆体を完全に溶解する極性溶剤が好ましく、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、テトラメチル尿素、ヘキサメチルリン酸トリアミド、γ−ブチロラクトン、δ−バレロラクトン、γ−バレロラクトン、シクロヘキサノン、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート、プロピレンカーボネート、乳酸エチル、１，３−ジメチル−２−イミダゾリジノン等が挙げられる。
これら溶剤は単独で用いてもよいし、２種以上を組み合わせて用いてもよい。(D) Component: Solvent The resin composition of the present invention may contain a solvent as the (d) component.
The solvent as component (d) is preferably a polar solvent that completely dissolves the polyimide precursor. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethyl Urea, hexamethylphosphoric triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolide Non etc. are mentioned.
These solvents may be used alone or in combination of two or more.
本発明の樹脂組成物の（ｄ）成分の含有量は、（ａ）成分１００重量部に対して５０〜５００質量部が好ましく、８０〜４００質量部がより好ましく、１００〜３００質量部がさらに好ましい。 The content of the component (d) in the resin composition of the present invention is preferably 50 to 500 parts by weight, more preferably 80 to 400 parts by weight, and further 100 to 300 parts by weight with respect to 100 parts by weight of the component (a). preferable.
（ｅ）成分：（ｂ）成分以外の光重合性化合物
本発明の樹脂組成物は、（ｅ）成分として（ｂ）成分以外の光重合性化合物を含んでもよい。前記光重合性化合物としては、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、スチレン、ジビニルベンゼン、４−ビニルトルエン、４−ビニルピリジン、Ｎ−ビニルピロリドン、２−ヒドロキシエチル（メタ）クリレート、１，３−（メタ）アクリロイルオキシ−２−ヒドロキシプロパン、メチレンビスアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−メチロールアクリルアミド等が挙げられる。これらは単独で用いてもよいし、２種類以上を組み合わせて用いてもよい。(E) Component: Photopolymerizable Compound Other than Component (b) The resin composition of the present invention may contain a photopolymerizable compound other than the component (b) as the component (e). Examples of the photopolymerizable compound include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, styrene, divinylbenzene, 4-vinyltoluene 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, , N- dimethyl acrylamide, N- methylol acrylamide. These may be used alone or in combination of two or more.
光重合性化合物を含有する場合の配合量は、（ａ）成分１００質量部に対して、１〜１００質量部とすることが好ましく、１０〜７５質量部とすることがより好ましく、３０〜５０質量部とすることがさらに好ましい。配合量が１質量部以上であれば、より良好な感光特性を付与することができ、１００質量部以下であれば、より硬化膜の耐熱性を向上することができる。 In the case of containing a photopolymerizable compound, the blending amount is preferably 1 to 100 parts by weight, more preferably 10 to 75 parts by weight, and more preferably 30 to 50 parts per 100 parts by weight of component (a). It is more preferable to set it as a mass part. If the blending amount is 1 part by mass or more, better photosensitive characteristics can be imparted, and if it is 100 parts by mass or less, the heat resistance of the cured film can be further improved.
上記（ａ）〜（ｅ）成分の他に、本発明の樹脂組成物は、良好な保存安定性を確保するために、ラジカル重合禁止剤又はラジカル重合抑制剤を含んでもよい。
具体的には、ｐ−メトキシフェノール、ジフェニル−ｐ−ベンゾキノン、ベンゾキノン、ハイドロキノン、ピロガロール、フェノチアジン、レゾルシノール、オルトジニトロベンゼン、パラジニトロベンゼン、メタジニトロベンゼン、フェナントラキノン、Ｎ−フェニル−２−ナフチルアミン、クペロン、２，５−トルキノン、タンニン酸、パラベンジルアミノフェノール、ニトロソアミン化合物等が挙げられる。これらは単独で用いてもよいし、２種類以上を組み合わせて用いてもよい。In addition to the above components (a) to (e), the resin composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to ensure good storage stability.
Specifically, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine,
樹脂組成物がラジカル重合禁止剤又はラジカル重合抑制剤を含有する場合の含有量としては、（ａ）成分１００質量部に対して、０．０１〜３０質量部であることが好ましく、０．０１〜１０質量部であることがより好ましく、０．０５〜５質量部であることがさらに好ましい。配合量が０．０１質量部以上であればより保存安定性が良好となり、３０質量部以下であれば、より硬化膜の耐熱性を向上することができる。 As content when a resin composition contains a radical polymerization inhibitor or a radical polymerization inhibitor, it is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of (a) component, More preferably, it is 10-10 mass parts, More preferably, it is 0.05-5 mass parts. If the blending amount is 0.01 parts by mass or more, the storage stability becomes better, and if it is 30 parts by mass or less, the heat resistance of the cured film can be further improved.
本発明の樹脂組成物は、硬化後のシリコン基板等への密着性をより向上させるために、有機シラン化合物をさらに含んでいてもよい。
上記有機シラン化合物としては、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノプロピルトリエトキシシラン、トリエトキシシリルプロピルエチルカルバメート、３−（トリエトキシシリル）プロピルコハク酸無水物、フェニルトリエトキシシラン、フェニルトリメトキシシラン、Ｎ―フェニル−３−アミノプロピルトリメトキシシラン、３−トリエトキシシリル−Ｎ−（１，３−ジメチルブチリデン）プロピルアミン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等が挙げられる。
有機シラン化合物の含有量は、所望の効果が得られるように適宜調整すればよい。The resin composition of the present invention may further contain an organosilane compound in order to further improve the adhesion to a cured silicon substrate or the like.
Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropyltri Methoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (2-hydroxyethyl) -3-amino Propyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-amino Examples include propyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
What is necessary is just to adjust suitably content of an organosilane compound so that a desired effect may be acquired.
＜硬化膜及びパターン硬化膜の製造方法＞
本発明の組成物を基材に塗布し、加熱硬化して得られる硬化膜の残留応力は、硬化膜の膜厚が１０μｍの場合において、３０ＭＰａ以下であることが好ましく、２７ＭＰａ以下であることがより好ましく、２５ＭＰａ以下であることがさらに好ましい。残留応力が３０ＭＰａ以下であれば、硬化後の膜厚が１０μｍとなるように膜を形成した場合に、ウエハの反りをより充分抑制することができ、ウエハの搬送や吸着固定において生じる不具合をより抑制することができる。<Method for producing cured film and patterned cured film>
The residual stress of the cured film obtained by applying the composition of the present invention to a substrate and heat-curing is preferably 30 MPa or less, and preferably 27 MPa or less when the thickness of the cured film is 10 μm. More preferably, it is more preferably 25 MPa or less. If the residual stress is 30 MPa or less, when the film is formed so that the film thickness after curing is 10 μm, the warpage of the wafer can be more sufficiently suppressed, and the problems caused in the conveyance and suction fixation of the wafer can be further reduced. Can be suppressed.
尚、残留応力は薄膜ストレス測定装置ＦＬＸ−２３２０（ＫＬＡ Ｔｅｎｃｏｒ社製）を用いて、ウエハの反り量を測定後、応力に換算する方法により測定することができる。 The residual stress can be measured by a method of converting the amount of warpage of the wafer into a stress after measuring the amount of warpage of the wafer using a thin film stress measuring apparatus FLX-2320 (manufactured by KLA Tencor).
本発明のパターン硬化膜は、上述の樹脂組成物から形成されるパターン硬化膜である。本発明のパターン硬化膜は上述の樹脂組成物が（ｃ）成分を含有するときに形成される。 The pattern cured film of this invention is a pattern cured film formed from the above-mentioned resin composition. The pattern cured film of this invention is formed when the above-mentioned resin composition contains (c) component.
また、本発明のパターン硬化膜の製造方法は、上述の樹脂組成物を基板上に塗布し乾燥して塗膜を形成する工程と、前記塗膜に活性光線を照射後、現像してパターン樹脂膜を得る工程と、前記パターン樹脂膜を加熱処理する工程とを含む。 Further, the method for producing a cured pattern film of the present invention includes a step of applying the above resin composition onto a substrate and drying to form a coating film, and irradiating the coating film with actinic rays, followed by development to form a pattern resin. A step of obtaining a film, and a step of heat-treating the patterned resin film.
以下、まずパターン硬化膜の製造方法の各工程について説明する。
本発明のパターン硬化膜の製造方法は、上述の樹脂組成物を基板上に塗布し乾燥して塗膜を形成する工程を含む。樹脂組成物を基材上に塗布する方法としては、浸漬法、スプレー法、スクリーン印刷法、スピンコート法等が挙げられる。基材としては、シリコンウエハ、金属基板、セラミック基板等が挙げられる。本発明の樹脂組成物は、低応力の硬化膜を形成可能であるので、１２インチ以上の大口径のシリコンウエハに好適に用いることができる。Hereinafter, each process of the manufacturing method of a pattern cured film is demonstrated first.
The manufacturing method of the pattern cured film of this invention includes the process of apply | coating the above-mentioned resin composition on a board | substrate, and drying and forming a coating film. Examples of the method for applying the resin composition on the substrate include dipping, spraying, screen printing, and spin coating. Examples of the substrate include a silicon wafer, a metal substrate, and a ceramic substrate. Since the resin composition of the present invention can form a low-stress cured film, it can be suitably used for a silicon wafer having a large diameter of 12 inches or more.
乾燥工程では、溶剤を加熱除去することによって、粘着性の無い塗膜を形成することができる。乾燥工程は、ＤＡＴＡＰＬＡＴＥ（Ｄｉｇｉｔａｌ Ｈｏｔｐｌａｔｅ、ＰＭＣ社製）等の装置を用いることができ、乾燥温度としては９０〜１３０℃が好ましく、乾燥時間としては１００〜４００秒が好ましい。 In the drying step, a solvent-free coating can be formed by removing the solvent by heating. For the drying step, an apparatus such as DATAPLATE (Digital Hotplate, manufactured by PMC) can be used, the drying temperature is preferably 90 to 130 ° C., and the drying time is preferably 100 to 400 seconds.
本発明のパターン硬化膜の製造方法は、前記工程で形成した塗膜に活性光線を照射後、現像してパターン樹脂膜を得る工程を含む。これにより所望のパターンが形成された樹脂膜を得ることができる。本発明の樹脂組成物はｉ線露光用に好適であるが、照射する活性光線としては、紫外線、遠紫外線、可視光線、電子線、Ｘ線等を用いることができる。 The manufacturing method of the pattern cured film of this invention includes the process of developing after irradiating the actinic ray to the coating film formed at the said process, and obtaining a pattern resin film. Thereby, a resin film on which a desired pattern is formed can be obtained. Although the resin composition of the present invention is suitable for i-line exposure, ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays, and the like can be used as the active rays to be irradiated.
現像液としては、特に制限はないが、１，１，１−トリクロロエタン等の難燃性溶媒、炭酸ナトリウム水溶液、テトラメチルアンモニウムハイドロオキサイド水溶液等のアルカリ水溶液、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、シクロペンタノン、γ−ブチロラクトン、酢酸エステル類等の良溶媒、これら良溶媒と低級アルコール、水、芳香族炭化水素等の貧溶媒との混合溶媒等が用いられる。現像後は必要に応じて貧溶媒等でリンス洗浄を行う。 The developer is not particularly limited, but is a flame retardant solvent such as 1,1,1-trichloroethane, an aqueous alkali solution such as an aqueous sodium carbonate solution and an aqueous tetramethylammonium hydroxide solution, N, N-dimethylformamide, dimethyl sulfoxide, Good solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates, etc., and these good solvents and poor solvents such as lower alcohols, water, and aromatic hydrocarbons A mixed solvent or the like is used. After development, rinsing with a poor solvent is performed as necessary.
本発明のパターン硬化膜の製造方法は、パターン樹脂膜を加熱処理する工程を含む。
この加熱処理は縦型拡散炉（光洋リンドバーク製）等の装置を用いることができ、加熱温度８０〜３００℃で行なうことが好ましく、加熱時間は５〜３００分間であることが好ましい。この工程によって、樹脂組成物中のポリイミド前駆体のイミド化を進行させてポリイミド樹脂を含有するパターン硬化膜を得ることができる。The manufacturing method of the pattern cured film of this invention includes the process of heat-processing a pattern resin film.
This heat treatment can be performed using an apparatus such as a vertical diffusion furnace (manufactured by Koyo Lindberg), and is preferably performed at a heating temperature of 80 to 300 ° C., and the heating time is preferably 5 to 300 minutes. By this step, imidation of the polyimide precursor in the resin composition can be advanced to obtain a patterned cured film containing a polyimide resin.
また、本発明の硬化膜は、上述の樹脂組成物から形成される硬化膜である。つまり、本発明の硬化膜はパターン形成されていない硬化膜であってもよい。
このようにして得られた本発明の硬化膜又はパターン硬化膜は、半導体装置の表面保護層、層間絶縁層、再配線層等として用いることができる。Moreover, the cured film of this invention is a cured film formed from the above-mentioned resin composition. That is, the cured film of the present invention may be a cured film that is not patterned.
The cured film or patterned cured film of the present invention thus obtained can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer or the like of a semiconductor device.
図１は、本発明の一実施形態である再配線構造を有する半導体装置の概略断面図である。
本実施形態の半導体装置は、多層配線構造を有している。層間絶縁層（層間絶縁膜）１の上にはＡ１配線層２が形成され、その上部にはさらに絶縁層（絶縁膜）３（例えばＰ−ＳｉＮ層）が形成され、さらに素子の表面保護層（表面保護膜）４が形成されている。配線層２のパット部５からは再配線層６が形成され、外部接続端子であるハンダ、金等で形成された導電性ボール７との接続部分である、コア８の上部まで伸びている。さらに表面保護層４の上には、カバーコート層９が形成されている。再配線層６は、バリアメタル１０を介して導電性ボール７に接続されているが、この導電性ボール７を保持するためには、カラー１１が設けられている。このような構造のパッケージを実装する際には、さらに応力を緩和するために、アンダーフィル１２を介することもある。FIG. 1 is a schematic cross-sectional view of a semiconductor device having a rewiring structure according to an embodiment of the present invention.
The semiconductor device of this embodiment has a multilayer wiring structure. An
本発明の硬化膜又はパターン硬化膜は、上記実施形態のカバーコート材、再配線用コア材、半田等のボール用カラー材、アンダーフィル材等に使用することができる。 The cured film or pattern cured film of the present invention can be used for the cover coating material, the core material for rewiring, the color material for balls such as solder, the underfill material, and the like.
本発明の電子部品は、本発明の硬化膜又はパターン硬化膜を用いたカバーコート、再配線用コア、半田等のボール用カラー、フリップチップ等で用いられるアンダーフィル等を有すること以外は特に制限されず、様々な構造をとることができる。 The electronic component of the present invention is particularly limited except that it has a cover coat using the cured film or pattern cured film of the present invention, a core for rewiring, a ball collar such as solder, an underfill used in flip chips, etc. Instead, it can take various structures.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically by way of examples.
合成例１（ピロメリット酸−ヒドロキシエチルメタクリレートジエステルの合成）
０．５リットルのポリ瓶中に、１６０℃の乾燥機で２４時間乾燥させたピロメリット酸二無水物４３．６２４ｇ（２００ｍｍｏｌ）とメタクリル酸２−ヒドロキシエチル５４．９１９ｇ（４０１ｍｍｏｌ）とハイドロキノン０．２２０ｇをＮ−メチルピロリドン３９４ｇに溶解し、１，８−ジアザビシクロウンデセンを触媒量添加後、室温下（２５℃）で２４時間撹拌し、エステル化を行うことで、ピロメリット酸−ヒドロキシエチルメタクリレートジエステル溶液を得た。この溶液をＰＭＤＡ（ＨＥＭＡ）溶液とする。Synthesis Example 1 (Synthesis of pyromellitic acid-hydroxyethyl methacrylate diester)
In a 0.5 liter plastic bottle, pyromellitic dianhydride 43.624 g (200 mmol), 2-hydroxyethyl methacrylate 54.919 g (401 mmol) and hydroquinone 0. 220 g is dissolved in 394 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture is stirred at room temperature (25 ° C.) for 24 hours to perform esterification, whereby pyromellitic acid-hydroxy An ethyl methacrylate diester solution was obtained. This solution is designated as PMDA (HEMA) solution.
合成例２（４，４’−オキシジフタル酸ジエステルの合成）
０．５リットルのポリ瓶中に、１６０℃の乾燥機で２４時間乾燥させた４，４’−オキシジフタル酸４９．６３４ｇ（１６０ｍｍｏｌ）とメタクリル酸２−ヒドロキシエチル４４．９７６ｇ（３２８ｍｍｏｌ）とハイドロキノン０．１７６ｇをＮ−メチルピロリドン３７８ｇに溶解し、１，８−ジアザビシクロウンデセンを触媒量添加後、室温下（２５℃）で４８時間撹拌し、エステル化を行い、４，４’−オキシジフタル酸−ヒドロキシエチルメタクリレートジエステル溶液を得た。この溶液をＯＤＰＡ（ＨＥＭＡ）溶液とする。Synthesis Example 2 (Synthesis of 4,4′-oxydiphthalic acid diester)
49.634 g (160 mmol) of 4,4′-oxydiphthalic acid, 44.976 g (328 mmol) of 2-hydroxyethyl methacrylate and hydroquinone 0 which were dried in a dryer of 160 ° C. for 24 hours in a 0.5 liter plastic bottle. 176 g was dissolved in 378 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25 ° C.) for 48 hours to perform esterification, and 4,4′-oxydiphthalate. An acid-hydroxyethyl methacrylate diester solution was obtained. This solution is defined as an ODPA (HEMA) solution.
合成例３（ポリマー１の合成）
撹拌機、温度計を備えた０．５リットルのフラスコ中に合成例１で得られたＰＭＤＡ（ＨＥＭＡ）溶液１９５．５６４ｇと合成例２で得られたＯＤＰＡ（ＨＥＭＡ）溶液５８．６５２ｇを入れ、その後、氷冷下で塩化チオニル２５．９ｇ（２１７．８ｍｍｏｌ）を反応溶液温度が１０度以下を保つように滴下漏斗を用いて滴下した。塩化チオニルの滴下が終了した後、氷冷下で２時間反応を行いＰＭＤＡ（ＨＥＭＡ）とＯＤＰＡ（ＨＥＭＡ）の酸クロリドの溶液を得た。次いで、滴下漏斗を用いて、２，２’−ビス（トリフルオロメチル）ベンジジン３１．６９６ｇ（９９．０ｍｍｏｌ）、ピリジン３４．４５７ｇ（４３５．６ｍｍｏｌ）、ハイドロキノン０．０７６ｇ（０．６９３ｍｍｏｌ）のＮ−メチルピロリドン９０．２１１ｇ溶液を氷冷化で反応溶液の温度が１０℃を超えないように注意しながら滴下した。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリアミド酸エステルを得た。標準ポリスチレン換算により求めた重量平均分子量は３４，０００であった。これをポリマー１とする。１ｇのポリマー１をＮ−メチルピロリドン１．５ｇに溶解させ、ガラス基板上にスピンコートで塗布し、１００℃のホットプレート上で１８０秒加熱し溶剤を揮発させて厚さ２０μｍの塗膜を形成した。この時、得られた塗膜のｉ線透過率は３０％であった。Synthesis Example 3 (Synthesis of Polymer 1)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 195.564 g of the PMDA (HEMA) solution obtained in Synthesis Example 1 and 58.652 g of the ODPA (HEMA) solution obtained in Synthesis Example 2 were placed. Thereafter, 25.9 g (217.8 mmol) of thionyl chloride was added dropwise by using a dropping funnel so as to keep the reaction solution temperature at 10 ° C. or lower under ice cooling. After the addition of thionyl chloride was completed, the reaction was carried out for 2 hours under ice cooling to obtain a solution of PMDA (HEMA) and ODPA (HEMA) acid chloride. Then, using a dropping funnel, 31.696 g (99.0 mmol) of 2,2′-bis (trifluoromethyl) benzidine, 34.457 g (435.6 mmol) of pyridine, 0.076 g (0.693 mmol) of hydroquinone -A solution of 90.211 g of methylpyrrolidone was added dropwise while cooling with ice so that the temperature of the reaction solution did not exceed 10 ° C. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. The weight average molecular weight determined by standard polystyrene conversion was 34,000. This is polymer 1. 1 g of polymer 1 is dissolved in 1.5 g of N-methylpyrrolidone, applied onto a glass substrate by spin coating, heated on a hot plate at 100 ° C. for 180 seconds to volatilize the solvent, and a 20 μm thick coating film is formed. did. At this time, the i-line transmittance of the obtained coating film was 30%.
ポリマー１のＧＰＣ法標準ポリスチレン換算により求めた重量平均分子量の測定条件は以下の通りであり、ポリマー０．５ｍｇに対して溶媒［ＴＨＦ／ＤＭＦ＝１／１（容積比）］１ｍＬの溶液を用いて測定した。 The measurement conditions of the weight average molecular weight calculated | required by GPC method standard polystyrene conversion of the polymer 1 are as follows, The solvent [THF / DMF = 1/1 (volume ratio)] 1mL solution was used with respect to 0.5 mg of polymers. Measured.
測定装置：検出器 株式会社日立製作所製Ｌ４０００ＵＶ
ポンプ：株式会社日立製作所製Ｌ６０００
株式会社島津製作所製Ｃ−Ｒ４Ａ Ｃｈｒｏｍａｔｏｐａｃ
測定条件：カラムＧｅｌｐａｃｋ ＧＬ−Ｓ３００ＭＤＴ−５ｘ２本
溶離液：ＴＨＦ／ＤＭＦ＝１／１（容積比）
ＬｉＢｒ（０．０３ｍｏｌ／Ｌ）、Ｈ３ＰＯ４（０．０６ｍｏｌ／Ｌ）
流速：１．０ｍＬ／ｍｉｎ、検出器：ＵＶ２７０ｎｍ
ポリマー１のｉ線透過率はＵ−３３１０ Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ（ＨＩＴＡＣＨＩ社製）を用いて測定した。Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H3PO4 (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm
The i-line transmittance of polymer 1 was measured using U-3310 Spectrophotometer (manufactured by HITACHI).
実施例１−６及び比較例１−４
（ａ）、（ｂ）、（ｃ）、（ｅ）の各成分を、表１に示す配合でＮ−メチルピロリドンに溶解して、樹脂組成物を調製し、下記の方法で解像度、残留応力及び膨潤率を評価した。結果を表１に示す。
尚、表１において、（ｂ）及び（ｃ）成分の各欄における括弧内の数字は、（ａ）成分１００質量部に対する添加量（質量部）を示す。また、溶剤はＮ−メチルピロリドンを用い、使用量は、いずれも（ａ）成分１００質量部に対して１．５倍（１５０質量部）で用いた。Example 1-6 and Comparative Example 1-4
Each component of (a), (b), (c), and (e) was dissolved in N-methylpyrrolidone with the formulation shown in Table 1 to prepare a resin composition. And the swelling rate was evaluated. The results are shown in Table 1.
In Table 1, the numbers in parentheses in each column of the components (b) and (c) indicate the amount (parts by mass) added to 100 parts by mass of the component (a). Further, N-methylpyrrolidone was used as the solvent, and the amount used was 1.5 times (150 parts by mass) with respect to 100 parts by mass of component (a).
（感光特性（解像度）の評価）
６インチシリコンウエハ上に調製した前記樹脂組成物をスピンコート法によって塗布し、１００℃のホットプレート上で３分間加熱し、溶剤を揮発させ、膜厚１０μｍの塗膜を得た。この塗膜をγ‐ブチロラクトン：酢酸ブチル＝７：３の混合溶媒に浸漬して完全に溶解するまでの時間の２倍を現像時間として設定した。同様の方法で得られた塗膜にフォトマスクを介して、ｉ線ステッパーＦＰＡ−３０００ｉＷ（キヤノン株式会社製）を用いて、ｉ線換算で３００ｍＪ／ｃｍ２露光を行い、ウエハをγ‐ブチロラクトン：酢酸ブチル＝７：３に浸漬してパドル現像した後、シクロペンタノンでリンス洗浄を行った。解像できたラインアンドスペースパターンのマスク寸法の最小値を解像度として評価した。(Evaluation of photosensitive characteristics (resolution))
The resin composition prepared on a 6-inch silicon wafer was applied by spin coating, heated on a hot plate at 100 ° C. for 3 minutes to evaporate the solvent, and a coating film having a thickness of 10 μm was obtained. The development time was set twice as long as the coating film was immersed in a mixed solvent of γ-butyrolactone: butyl acetate = 7: 3 and completely dissolved. An i-line stepper FPA-3000iW (manufactured by Canon Inc.) is used to expose the coated film obtained in the same manner through a photomask to 300 mJ / cm 2 in terms of i-line, and the wafer is subjected to γ-butyrolactone: After dipping in butyl acetate = 7: 3 for paddle development, rinsing with cyclopentanone was performed. The minimum mask dimension of the line and space pattern that could be resolved was evaluated as the resolution.
（残留応力の測定）
得られた樹脂組成物を、６インチシリコンウエハ上にスピンコート法によって塗布し、１００℃のホットプレート上で３分間加熱し、溶剤を揮発させ硬化後膜厚が１０μｍとなる塗膜を得た。これを、縦型拡散炉（光洋リンドバーク製）を用いて、窒素雰囲気下、２７０℃で４時間加熱硬化して、ポリイミド膜を得た。硬化後のポリイミド膜の残留応力は薄膜ストレス測定装置ＦＬＸ−２３２０（ＫＬＡＴｅｎｃｏｒ社製）を用いて室温において測定した。(Measurement of residual stress)
The obtained resin composition was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100 ° C. for 3 minutes, and the solvent was evaporated to obtain a coating film having a thickness of 10 μm after curing. . This was heat-cured at 270 ° C. for 4 hours in a nitrogen atmosphere using a vertical diffusion furnace (manufactured by Koyo Lindberg) to obtain a polyimide film. The residual stress of the cured polyimide film was measured at room temperature using a thin film stress measuring apparatus FLX-2320 (manufactured by KLA Tencor).
（膨潤率の測定）
得られた樹脂組成物を、６インチシリコンウエハ上にスピンコート法によって塗布し、１００℃のホットプレート上で３分間加熱し、溶剤を揮発させ硬化後膜厚が１０μｍとなる塗膜を得た。これを、縦型拡散炉（光洋リンドバーク製）を用いて、窒素雰囲気下、２７０℃で４時間加熱硬化して、ポリイミド膜を得た。基板上に作製されたポリイミド膜を７０℃のＮ−メチルピロリドンに浸漬し、２０分加熱を行った。Ｎ−メチルピロリドンに浸漬したサンプルを蒸留水ですすいだ後、膜厚を測定した。Ｎ−メチルピロリドン浸漬前後の膜厚変化から、膨潤率（％）を算出した。(Measurement of swelling rate)
The obtained resin composition was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100 ° C. for 3 minutes, and the solvent was evaporated to obtain a coating film having a thickness of 10 μm after curing. . This was heat-cured at 270 ° C. for 4 hours in a nitrogen atmosphere using a vertical diffusion furnace (manufactured by Koyo Lindberg) to obtain a polyimide film. The polyimide film produced on the substrate was immersed in N-methylpyrrolidone at 70 ° C. and heated for 20 minutes. The sample immersed in N-methylpyrrolidone was rinsed with distilled water, and the film thickness was measured. The swelling ratio (%) was calculated from the change in film thickness before and after immersion in N-methylpyrrolidone.
表１において（ｂ）成分は以下のとおりである。
Ａ９３００（エトキシ化イソシアヌル酸トリアクリレート、新中村化学株式会社製、商品名）In Table 1, the component (b) is as follows.
A9300 (ethoxylated isocyanuric acid triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)
表１において（ｃ）成分は下記の化合物である。
Ｃ１：１，２−オクタンジオン，１−［４−（フェニルチオ）フェニル−，２−（ｏ−ベンゾイルオキシム）］（ＢＡＳＦ株式会社製、商品名「ＩＲＧＡＣＵＲＥ ＯＸＥ−０１」）
Ｃ２：アデカクルーズＮＣＩ−９３０（株式会社ＡＤＥＫＡ製、商品名）In Table 1, component (c) is the following compound.
C1: 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (o-benzoyloxime)] (trade name “IRGACURE OXE-01” manufactured by BASF Corporation)
C2: Adeka Cruise NCI-930 (made by ADEKA, trade name)
表１において（ｅ）成分は、テトラエチレングリコールジメタクリレートである。
また、アルミキレートＡ（ｗ）は、アルミニウムトリスアセチルアセトネート（川研ファインケミカル社製）である。In Table 1, component (e) is tetraethylene glycol dimethacrylate.
Aluminum chelate A (w) is aluminum trisacetylacetonate (manufactured by Kawaken Fine Chemical Co., Ltd.).
実施例では、フッ素を含有する剛直なポリイミドにイソシアヌル骨格を有する化合物を添加することで、３０ＭＰａ以下の低い応力を保ったまま、膨潤率が１０％以下となっている。一方、比較例では、組成物がイソシアヌル骨格を有する化合物を含まない場合、フッ素含有ポリイミドは２０％以上の大きな膨潤率となっている。また、比較例３及び４では、アルミキレート化合物を添加したが、硬化温度が低いため、薬液耐性改善効果は得られなかった。 In the examples, by adding a compound having an isocyanuric skeleton to rigid polyimide containing fluorine, the swelling rate is 10% or less while maintaining a low stress of 30 MPa or less. On the other hand, in the comparative example, when the composition does not contain a compound having an isocyanuric skeleton, the fluorine-containing polyimide has a large swelling ratio of 20% or more. In Comparative Examples 3 and 4, an aluminum chelate compound was added, but since the curing temperature was low, the effect of improving chemical resistance was not obtained.
本発明の樹脂組成物は、半導体装置等の電子部品を形成する、カバーコート材、再配線用コア材、ハンダ等のボール用カラー材、アンダーフィル材等、いわゆるパッケージ用途に使用することができる。 The resin composition of the present invention can be used for so-called package applications such as cover coat materials, core materials for rewiring, color materials for balls such as solder, underfill materials, etc., which form electronic parts such as semiconductor devices. .
上記に本発明の実施形態及び／又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び／又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.
Claims (15)
（ａ）下記式（１）で表される構造単位を有するポリイミド前駆体、
（ｂ）エチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物The resin composition containing the following (a) component and (b) component.
(A) a polyimide precursor having a structural unit represented by the following formula (1),
(B) Photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014023519 | 2014-02-10 | ||
| JP2014023519 | 2014-02-10 | ||
| PCT/JP2015/000357 WO2015118836A1 (en) | 2014-02-10 | 2015-01-28 | Resin composition containing polyimide precursor, method for manufacturing cured film, and electronic component |
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| JP2019201268A Division JP6888660B2 (en) | 2014-02-10 | 2019-11-06 | Resin composition containing polyimide precursor, method for manufacturing cured film and electronic components |
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| JP2019201268A Active JP6888660B2 (en) | 2014-02-10 | 2019-11-06 | Resin composition containing polyimide precursor, method for manufacturing cured film and electronic components |
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| KR (1) | KR20160124082A (en) |
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| JP6297757B2 (en) * | 2015-08-21 | 2018-03-20 | 旭化成株式会社 | Photosensitive resin composition, method for producing polyimide, and semiconductor device |
| JP6917187B2 (en) * | 2016-05-10 | 2021-08-11 | 住友化学株式会社 | Optical film and flexible devices using it |
| WO2020080216A1 (en) * | 2018-10-19 | 2020-04-23 | 富士フイルム株式会社 | Cured film production method, resin composition, cured film, laminate body production method, and semiconductor device manufacturing method |
| TW202212423A (en) * | 2020-06-05 | 2022-04-01 | 日商富士軟片股份有限公司 | Resin composition, production method therefor, and method for producing composition for pattern formation |
| WO2024070713A1 (en) * | 2022-09-30 | 2024-04-04 | 富士フイルム株式会社 | Resin composition, insulating film and method for producing interlayer insulating film for redistribution layers |
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- 2015-01-28 CN CN201580008033.3A patent/CN106462065A/en active Pending
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| CN106462065A (en) | 2017-02-22 |
| TW201533157A (en) | 2015-09-01 |
| JP6888660B2 (en) | 2021-06-16 |
| KR20160124082A (en) | 2016-10-26 |
| JP2020037699A (en) | 2020-03-12 |
| WO2015118836A1 (en) | 2015-08-13 |
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