CN117836339A - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- CN117836339A CN117836339A CN202280057436.7A CN202280057436A CN117836339A CN 117836339 A CN117836339 A CN 117836339A CN 202280057436 A CN202280057436 A CN 202280057436A CN 117836339 A CN117836339 A CN 117836339A
- Authority
- CN
- China
- Prior art keywords
- resin composition
- cyclic olefin
- olefin polymer
- group
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011342 resin composition Substances 0.000 title claims abstract description 145
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 129
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 239000003431 cross linking reagent Substances 0.000 claims description 61
- 125000003118 aryl group Chemical group 0.000 claims description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 125000000962 organic group Chemical group 0.000 claims description 5
- 239000011347 resin Substances 0.000 abstract description 87
- 229920005989 resin Polymers 0.000 abstract description 87
- 150000003997 cyclic ketones Chemical class 0.000 abstract description 30
- 238000000059 patterning Methods 0.000 abstract description 27
- 239000010408 film Substances 0.000 description 98
- 150000003254 radicals Chemical class 0.000 description 69
- 229920000642 polymer Polymers 0.000 description 53
- -1 cyclic olefin Chemical class 0.000 description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- 238000006011 modification reaction Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 23
- 239000003607 modifier Substances 0.000 description 23
- 239000000126 substance Substances 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 238000005984 hydrogenation reaction Methods 0.000 description 20
- 238000012986 modification Methods 0.000 description 19
- 230000004048 modification Effects 0.000 description 19
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000000178 monomer Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 15
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 125000002947 alkylene group Chemical group 0.000 description 13
- 238000009826 distribution Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000007810 chemical reaction solvent Substances 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 8
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 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 7
- FFHTYJZGMFIFII-UHFFFAOYSA-N dodec-4-ene Chemical compound [CH2]CCCCCCC=CCCC FFHTYJZGMFIFII-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 2
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 description 2
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 description 2
- RVFOVZRXGSBMFS-UHFFFAOYSA-N C=C.C1CCCCCC=CCCCC1.C1CCCCCC=CCCCC1.C1CCCCCC=CCCCC1.C1CCCCCC=CCCCC1 Chemical compound C=C.C1CCCCCC=CCCCC1.C1CCCCCC=CCCCC1.C1CCCCCC=CCCCC1.C1CCCCCC=CCCCC1 RVFOVZRXGSBMFS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 150000008365 aromatic ketones Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- LJKNRSBEKUSSIE-UHFFFAOYSA-N hept-2-ene Chemical compound [CH2]CCCC=CC LJKNRSBEKUSSIE-UHFFFAOYSA-N 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 2
- NPENBPVOAXERED-UHFFFAOYSA-N (4-benzoylphenyl)-phenylmethanone Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 NPENBPVOAXERED-UHFFFAOYSA-N 0.000 description 1
- JBVMSEMQJGGOFR-FNORWQNLSA-N (4e)-4-methylhexa-1,4-diene Chemical compound C\C=C(/C)CC=C JBVMSEMQJGGOFR-FNORWQNLSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- LLPLOWFYJGZIBV-UHFFFAOYSA-N 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene-2-methanol Chemical compound C1C(C23)C=CC1C3C1CC2CC1CO LLPLOWFYJGZIBV-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 description 1
- ZIJDEADTCQKATN-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)-5-propyl-1,3,5-triazinane-2,4,6-trione Chemical compound CCCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O ZIJDEADTCQKATN-UHFFFAOYSA-N 0.000 description 1
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- ZENYUPUKNXGVDY-UHFFFAOYSA-N 1,4-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=C(C(C)=C)C=C1 ZENYUPUKNXGVDY-UHFFFAOYSA-N 0.000 description 1
- IZXSWEQCVDBMOL-UHFFFAOYSA-N 1-(bromomethyl)-2-ethenylbenzene Chemical compound BrCC1=CC=CC=C1C=C IZXSWEQCVDBMOL-UHFFFAOYSA-N 0.000 description 1
- WFCJSNUJPWSKNE-UHFFFAOYSA-N 1-(bromomethyl)-3-ethenylbenzene Chemical compound BrCC1=CC=CC(C=C)=C1 WFCJSNUJPWSKNE-UHFFFAOYSA-N 0.000 description 1
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- DSGCOGYKYQBKCK-UHFFFAOYSA-N 1-[(4-ethenylphenyl)methylsulfonyl]-4-methylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)CC1=CC=C(C=C)C=C1 DSGCOGYKYQBKCK-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- GLIWMVHZVCUEHQ-UHFFFAOYSA-N 1-ethenyl-2-(fluoromethyl)benzene Chemical compound FCC1=CC=CC=C1C=C GLIWMVHZVCUEHQ-UHFFFAOYSA-N 0.000 description 1
- YJIKNULEWINHPE-UHFFFAOYSA-N 1-ethenyl-2-(iodomethyl)benzene Chemical compound ICC1=CC=CC=C1C=C YJIKNULEWINHPE-UHFFFAOYSA-N 0.000 description 1
- BFMVOABFAXMVAG-UHFFFAOYSA-N 1-ethenyl-2-[(4-methylphenyl)sulfonylmethyl]benzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)CC1=CC=CC=C1C=C BFMVOABFAXMVAG-UHFFFAOYSA-N 0.000 description 1
- XIGIIWLUYWHNRO-UHFFFAOYSA-N 1-ethenyl-3-(fluoromethyl)benzene Chemical compound FCC1=CC=CC(C=C)=C1 XIGIIWLUYWHNRO-UHFFFAOYSA-N 0.000 description 1
- QXWGKIRJWBULQD-UHFFFAOYSA-N 1-ethenyl-3-(iodomethyl)benzene Chemical compound ICC1=CC=CC(C=C)=C1 QXWGKIRJWBULQD-UHFFFAOYSA-N 0.000 description 1
- WNLYONPBCCQPHU-UHFFFAOYSA-N 1-ethenyl-4-(fluoromethyl)benzene Chemical compound FCC1=CC=C(C=C)C=C1 WNLYONPBCCQPHU-UHFFFAOYSA-N 0.000 description 1
- KFZYYXVIZOVAFO-UHFFFAOYSA-N 1-ethenyl-4-(iodomethyl)benzene Chemical compound ICC1=CC=C(C=C)C=C1 KFZYYXVIZOVAFO-UHFFFAOYSA-N 0.000 description 1
- UCOVOVVMCCOUSR-UHFFFAOYSA-N 1-ethenyl-4-(methylsulfonylmethyl)benzene Chemical compound CS(=O)(=O)CC1=CC=C(C=C)C=C1 UCOVOVVMCCOUSR-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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Abstract
The present invention aims to provide a resin composition comprising a cyclic olefin polymer, which is capable of forming a resin film having excellent patterning characteristics when cyclic ketone is used as a developer. The resin composition of the present invention comprises a cyclic olefin polymer and a radical initiator. Here, the cyclic olefin polymer contains a prescribed structural unit (I) and a prescribed structural unit (II). When the amount of all the structural units contained in the cyclic olefin polymer is 100 mol%, the total of the content of the structural unit (I) and the content of the structural unit (II) in the cyclic olefin polymer is 80 mol% or more.
Description
Technical Field
The present invention relates to a resin composition.
Background
Conventionally, electronic components such as integrated circuit devices and organic EL devices are provided with various resin films as protective films for preventing deterioration and damage of the components themselves, planarization films for planarizing the device surfaces and wirings, electrical insulating films for maintaining electrical insulation, pixel separation films for separating light emitting portions, optical films for condensing and diffusing light, and the like.
In recent years, various cyclic olefin polymers having excellent properties have been attracting attention as a resin material constituting such a resin film. For example, patent document 1 discloses a resin composition comprising a cyclic olefin polymer having a plurality of crosslinkable double bonds in a side chain portion, a predetermined polyphenylene ether, triallyl isocyanurate and/or triallyl cyanurate, and an organic peroxide. Further, according to patent document 1, a resin film having a low dielectric loss tangent can be formed by using the resin composition.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2018-39950.
Disclosure of Invention
Problems to be solved by the invention
Here, a resin film is generally given a desired pattern shape according to its use. In addition, cyclic ketones such as cyclopentanone are widely used as a developer in patterning. However, even if a resin film formed using the above-mentioned conventional resin composition is exposed, the resin film after exposure is developed with cyclic ketone, and it is difficult to impart a desired pattern shape to the resin film because the cyclic olefin polymer is hardly soluble in cyclic ketone.
That is, in the above-mentioned conventional resin composition containing a cyclic olefin polymer, there is room for further improvement in terms of improving the patterning characteristics when cyclic ketone is used as a developer for a resin film formed from the resin composition.
Accordingly, an object of the present invention is to provide a resin composition containing a cyclic olefin polymer, which is capable of forming a resin film excellent in patterning characteristics when cyclic ketone is used as a developer.
Solution for solving the problem
The present inventors have conducted intensive studies in order to achieve the above object. Then, the present inventors have newly found that, when a resin composition comprising a cyclic olefin polymer and a radical initiator is used, the cyclic olefin polymer comprises two predetermined structural units and the total content ratio of the two structural units is equal to or greater than a predetermined value, a resin film having excellent patterning characteristics when cyclic ketone is used as a developer can be formed, and completed the present invention.
That is, an object of the present invention is to advantageously solve the above-mentioned problems, and according to the present invention, there is provided the following resin compositions [1] to [5 ].
[1] A resin composition comprising a cyclic olefin polymer and a radical initiator, wherein the cyclic olefin polymer comprises a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II), and the total of the content of the structural unit (I) and the content of the structural unit (II) in the cyclic olefin polymer is 80 mol% or more based on 100 mol% of the total amount of the structural units contained in the cyclic olefin polymer.
[ chemical formula 1]
In the formula (I), R 1 ～R 4 At least one of them is a radical crosslinkable group, R not being a radical crosslinkable group 1 ～R 4 R is independently a hydrogen atom, an alkyl group or an aromatic ring group, and is not a radical crosslinkable group 1 ～R 4 Can form a ring together, m is an integer of 0 to 4 inclusive.
[ chemical formula 2]
In the formula (II), R 5 ～R 8 At least one of them is an aromatic ring group, or R 5 ～R 8 Two of (a) together form an aromatic ring-containing structure, R is not an aromatic ring group and does not form an aromatic ring-containing structure 5 ～R 8 Each independently represents a hydrogen atom or an alkyl group, and n is an integer of 0 to 4 inclusive.
According to the resin composition, a resin film having excellent patterning characteristics when cyclic ketone is used as a developer can be formed.
In the present specification, the "content ratio" of each structural unit contained in the polymer can be used 1 H-NMR、 13 The measurement is performed by Nuclear Magnetic Resonance (NMR) such as C-NMR.
[2] The resin composition according to the above [1], wherein the content of the structural unit (II) in the cyclic olefin polymer is 70 mol% or more, based on 100 mol% of the total structural units contained in the cyclic olefin polymer.
If the content of the structural unit (II) in the cyclic olefin polymer is 70 mol% or more, the dielectric loss tangent of a resin film formed from the resin composition can be reduced and the mechanical strength can be improved.
[3] The resin composition according to the above [1] or [2], wherein the radical crosslinkable group has at least one of a styrene-based skeleton and an acrylate skeleton.
If the structural unit (I) contains a radical crosslinkable group having a styrene-based skeleton, the dielectric loss tangent of a resin film formed from the resin composition can be reduced, and further, the patterning characteristics in the case of using cyclic ketone as a developer can be further improved for the resin film. Further, if the structural unit (I) contains a radical crosslinkable group having an acrylate skeleton, the dielectric loss tangent of a resin film formed from the resin composition can be reduced and the stretchability can be improved, and further, the patterning characteristics in the case of using cyclic ketone as a developer can be further improved for the resin film.
In the present specification, the term "having a styrene skeleton" as a radical crosslinkable group means that the radical crosslinkable group contains "CH" 2 =ch-Ph- (Ph is phenylene, and some or all of hydrogen atoms in the formula may be substituted with an optional substituent) ". In the present specification, the "group having a styrene-based skeleton" is not an "aromatic ring group" but a "radical crosslinkable group".
In the present specification, the term "having an acrylate skeleton" means that the radical crosslinkable group contains "CH" 2 The chemical structure represented by =ch-C (=o) -O- (some or all of hydrogen atoms in the formula may be substituted with an arbitrary substituent).
[4] The resin composition according to any one of the above [1] to [3], wherein the resin composition further comprises a crosslinking agent having at least two polymerizable unsaturated bonds.
If a resin composition containing a crosslinking agent having at least two polymerizable unsaturated bonds (hereinafter sometimes simply referred to as "crosslinking agent") in addition to the above-mentioned cyclic olefin polymer and radical initiator is used, it is possible to reduce the dielectric loss tangent of a resin film formed from the resin composition and to improve the stretchability.
In the present specification, a polymer containing a structural unit derived from a cyclic olefin does not belong to a "crosslinking agent" but to a "cyclic olefin polymer" even when the polymer has at least two polymerizable unsaturated bonds.
[5] The resin composition according to the above [4], wherein the crosslinking agent comprises at least one of a crosslinking agent (III) represented by the following formula (III) and a crosslinking agent (IV) represented by the following formula (IV).
[ chemical formula 3]
[ chemical formula 4]
In the formula (IV), A is a divalent organic group, and a and b are integers of 0 to 300 inclusive. In addition, a and b may be the same or different, but the case where only one of a and b is 0 is not included.
If a resin composition containing the crosslinking agent (III) and/or the crosslinking agent (IV) as the crosslinking agent is used, it is possible to further reduce the dielectric loss tangent of a resin film formed from the resin composition and further improve the stretchability.
Effects of the invention
According to the resin composition comprising a cyclic olefin polymer of the present invention, a resin film excellent in patterning characteristics when a cyclic ketone is used as a developer can be formed.
Detailed Description
The resin composition of the present invention is not particularly limited, and can be used for forming a resin film that can be provided in electronic parts such as integrated circuit devices, organic EL devices, and semiconductor packages. In particular, the resin composition of the present invention can be preferably used for producing an insulating organic film such as an organic EL, a semiconductor package, a printed wiring board, or a solder resist. The resin composition of the present invention can be preferably used as a negative photosensitive resin composition having a low solubility in a developer at an exposed portion and remaining at the exposed portion by development. The active energy ray used for exposing the resin film formed using the resin composition of the present invention is not particularly limited, and examples thereof include: light of a single wavelength such as ultraviolet rays, g rays, h rays, i rays, and the like, light of KrF excimer laser, arF excimer laser, and the like, and particle beams such as electron beams.
(resin composition)
The resin composition of the present invention needs to contain a cyclic olefin polymer and a radical initiator, and can optionally contain at least one selected from a crosslinking agent, a solvent, and other additive components.
< Cyclic olefin Polymer >
The cyclic olefin polymer contained in the resin composition of the present invention is a polymer capable of undergoing a crosslinking reaction by using radicals generated by irradiation of active energy rays in the presence of a radical initiator.
Here, the cyclic olefin polymer requires: the total of the content of the structural unit (I) and the content of the structural unit (II) in the cyclic olefin polymer is 80 mol% or more, based on 100 mol% of the total structural units contained in the cyclic olefin polymer.
[ chemical formula 5]
In the formula (I), R 1 ～R 4 At least one of them is a radical crosslinkable group, R not being a radical crosslinkable group 1 ～R 4 R is independently a hydrogen atom, an alkyl group or an aromatic ring group, and is not a radical crosslinkable group 1 ～R 4 Can form a ring together, m is an integer of 0 to 4 inclusive.
[ chemical formula 6]
In the formula (II), R 5 ～R 8 At least one of them is an aromatic ring group, or R 5 ～R 8 Two of (a) together form an aromatic ring-containing structure, R is not an aromatic ring group and does not form an aromatic ring-containing structure 5 ～R 8 Each independently represents a hydrogen atom or an alkyl group, and n is an integer of 0 to 4 inclusive.
Further, if the resin composition of the present invention containing the cyclic olefin polymer having the above composition is used, a resin film excellent in patterning characteristics when cyclic ketone is used as a developer can be formed.
The reason why the resin film formed using the resin composition of the present invention is excellent in patterning characteristics when cyclic ketone is used as a developer is not clear, but is presumed as follows.
First, a resin film obtained by using a resin composition containing a cyclic olefin polymer having the above composition is less likely to cause turbidity due to phase separation, and scattering of active energy rays can be suppressed at the time of exposure. In addition, the cyclic olefin polymer having the above composition contained in the unexposed portion of the resin film has high solubility in cyclic ketone used as a developer. It is considered that the use of the resin composition of the present invention can form a resin film having excellent patterning characteristics when cyclic ketone is used as a developer, due to the contribution of the cyclic olefin polymer having such characteristics.
Structural unit (I)
In the structural unit (I) shown in the formula (I), R 1 ～R 4 At least one of them is a radical crosslinkable group. Further, R is not a radical crosslinkable group 1 ～R 4 R is independently a hydrogen atom, an alkyl group or an aromatic ring group, and is not a radical crosslinkable group 1 ～R 4 Can together form a ring. M is an integer of 0 to 4 inclusive.
The cyclic olefin polymer may contain only one structural unit (I) or may contain a plurality of structural units (I).
[ radical crosslinkable group ]
Here, R can be formed as 1 ～R 4 The radical crosslinkable group (c) is not particularly limited as long as it has a carbon-carbon unsaturated bond (in particular, an ethylenic unsaturated bond) and has a molecular skeleton capable of undergoing radical reaction due to a radical generated by a radical initiator. The radical crosslinkable group is preferably a radical crosslinkable group having a styrene skeleton or a radical crosslinkable group having an acrylate skeleton.
Radical crosslinkable group having styrene-based skeleton
If the structural unit (I) of the cyclic olefin polymer has a radical crosslinkable group having a styrene-based skeleton, it is presumed that the dielectric loss tangent of the resin film can be reduced because the proportion of polar atoms in the structural unit (I) is reduced. Further, with respect to the resin film, the patterning characteristics when cyclic ketone is used as the developer can be further improved.
Examples of the radical crosslinkable group having a styrene-based skeleton include a group represented by the following formula (V).
[ chemical formula 7]
In the formula (V), X and Z are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, Y is an oxygen atom or a sulfur atom, R 9 P is an integer of 0 to 4 inclusive, and is a hydrogen atom or a substituent.
In the formula (V), the alkylene group having 1 to 10 carbon atoms which can be used as X and Z is not particularly limited, but is preferably a chain alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutyl group, etc., more preferably a linear alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, an n-butylene group, etc., still more preferably a linear alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, etc., particularly preferably a methylene group.
In the formula (V), R is as follows 9 Examples of the substituent(s) include, but are not particularly limited to, alkyl groups such as methyl and ethyl, and halogen groups such as fluoro and chloro.
In the formula (V), p is preferably 0, that is, phenylene (-C) constituting the styrene-based skeleton is preferable 6 H 4 (-) has no substituent.
Radical crosslinkable groups having acrylate skeletons
If the structural unit (I) of the cyclic olefin polymer has a radical crosslinkable group having an acrylate skeleton, the dielectric loss tangent of a resin film formed from the resin composition can be reduced and the stretchability can be improved. Further, with respect to the resin film, the patterning characteristics when cyclic ketone is used as the developer can be further improved.
Examples of the radical crosslinkable group having an acrylate skeleton include a group represented by the following formula (VI).
[ chemical formula 8]
In the formula (VI), G is an alkylene group having 1 to 10 carbon atoms, R 10 Is a hydrogen atom or an alkyl group.
In the radical crosslinkable group represented by the formula (VI), a substituted or unsubstituted acryl group is bonded to the cyclic olefin structure via an alkylene group represented by G, and thus the motility of the acryl group is improved. The crosslinking reactivity of the acryl group is improved due to the improvement of the mobility. It is presumed that, for the above reasons, if the cyclic olefin polymer having a radical crosslinkable group represented by the formula (VI) is used, the dielectric loss tangent of a resin film formed from the resin composition can be reduced and the stretchability can be improved, and further, the patterning characteristics in the case of using cyclic ketone as a developer can be further improved for the resin film.
In the formula (VI), the alkylene group having 1 to 10 carbon atoms which can be used as G is not particularly limited, but is preferably a chain alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutyl group, etc., more preferably a linear alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, an n-butylene group, etc., still more preferably a linear alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, etc., particularly preferably a methylene group.
In the formula (VI), R is as an element 10 The alkyl group of (2) is not particularly limited, and examples thereof include a C-atom numberAlkyl of 1 to 5 inclusive. As a constituent R 10 Particularly preferably methyl or ethyl.
[ Structure other than radical-crosslinkable group ]
In the formula (I), R other than the radical crosslinking group can be formed 1 ～R 4 The alkyl group of (a) is not particularly limited, and examples thereof include an alkyl group having 1 to 5 carbon atoms.
In the formula (I), R other than the radical crosslinking group can be formed 1 ～R 4 The aromatic ring group of (a) is not particularly limited as long as it is not a radical crosslinkable group, and examples thereof include an aromatic ring group having 4 to 30 carbon atoms such as a phenyl group, a naphthyl group, a fluorenyl group, an anthracenyl group, a triphenylenyl group, and a pyrenyl group.
In addition, R is other than radical crosslinking group 1 ～R 4 The structure of the two groups together forming a ring is not particularly limited, and examples thereof include a carbocyclic ring having a monocyclic structure or a polycyclic structure.
In formula (I), m is an integer of 0 to 4, preferably 0, 1 or 2, more preferably 0 or 1.
[ preferred Structure of structural Unit (I) ]
Furthermore, the structural unit (I) is preferably of the formula (I), R 1 ～R 4 One of them is a radical crosslinkable group, and the other is a hydrogen atom. This is because if the structural unit (I) has such a structure, synthesis is easier and the production efficiency of the resin composition is improved.
[ proportion of structural Unit (I) contained ]
Here, when the amount of all the structural units contained in the cyclic olefin polymer is set to 100 mol%, the content of the structural unit (I) in the cyclic olefin polymer is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, particularly preferably 15 mol% or more, preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 20 mol% or less. If the content of the structural unit (I) in the cyclic olefin polymer is 1 mol% or more, the patterning characteristics can be further improved when cyclic ketone is used as a developer for a resin film formed from the resin composition. On the other hand, if the content of the structural unit (I) in the cyclic olefin polymer is 60 mol% or less, the dielectric loss tangent of the resin film formed from the resin composition can be reduced and the stretchability can be improved.
Structural unit (II)
In the structural unit (II) represented by the above formula (II), R 5 ～R 8 At least one of them is an aromatic ring group, or R 5 ～R 8 Two of (a) together form an aromatic ring-containing structure, R is not an aromatic ring group and does not form an aromatic ring-containing structure 5 ～R 8 Each independently represents a hydrogen atom or an alkyl group, and n is an integer of 0 to 4 inclusive.
The cyclic olefin polymer may contain only one structural unit (II) or may contain a plurality of structural units (II).
Here, R is represented by the formula (II) 5 ～R 8 The aromatic ring group of (a) is not particularly limited, and examples thereof include an aromatic ring group having 4 to 30 carbon atoms. Examples of the aromatic ring group having 4 to 30 carbon atoms include phenyl, naphthyl, fluorenyl, anthracenyl, triphenylenyl, and pyrenyl.
In addition, R is as formula (II) 5 ～R 8 Examples of the aromatic ring in the aromatic ring-containing structure formed by two of these compounds include aromatic hydrocarbon rings such as benzene rings and naphthalene rings. The aromatic ring-containing structure may contain only one aromatic ring or may contain a plurality of aromatic rings. In the case where the aromatic ring-containing structure has a plurality of aromatic rings, the plurality of aromatic rings may be the same type of aromatic ring or may be different types of aromatic ring. And R is 5 ～R 8 The aromatic ring-containing structure formed by the two of these are not particularly limited, and the total number of carbon atoms is preferably 7 to 60. Furthermore, the aromatic ring-containing structure is preferably composed of only carbon atoms.
In the formula (II), R is not an aromatic ring group and is not an aromatic ring-containing structure 5 ～R 8 The alkyl group of (2) is not particularly limited, and examples thereof include those which can constitute R as described above 1 ～R 4 Alkyl groups identical to the alkyl groups of (a).
Further, in the formula (II), n is an integer of 0 to 4, preferably 0, 1 or 2, more preferably 0 or 1, as described above.
[ preferred Structure of structural Unit (II) ]
Further, from the viewpoints of reducing the dielectric loss tangent of a resin film formed from the resin composition and improving the stretchability, and further improving the patterning characteristics of the resin film when cyclic ketone is used as a developer, the structural unit (II) is preferably R 5 ～R 8 One of them is an aromatic ring group and the other is a hydrogen atom, and R 5 And R is 6 One of which is with R 7 And R is 8 Together, one of them forms an aromatic ring-containing structure (e.g., a benzene ring-containing structure) and the other is a hydrogen atom, and the latter is more preferable.
[ proportion of structural Unit (II) contained ]
Here, when the amount of all the structural units contained in the cyclic olefin polymer is set to 100 mol%, the content of the structural unit (II) in the cyclic olefin polymer is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, preferably 99 mol% or less, more preferably 95 mol% or less, and still more preferably 90 mol% or less. If the content of the structural unit (II) in the cyclic olefin polymer is 10 mol% or more, the dielectric loss tangent of a resin film formed from the resin composition can be reduced and the mechanical strength (tensile strength) can be improved. On the other hand, if the content of the structural unit (II) in the cyclic olefin polymer is 99 mol% or less, the patterning characteristics when cyclic ketone is used as a developer can be further improved for a resin film formed from the resin composition.
The total content ratio of structural units (I) and (II)
In the cyclic olefin polymer, when the total amount of the structural units contained in the cyclic olefin polymer is 100 mol%, the total of the content of the structural units (I) and the content of the structural units (II) is 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, still more preferably 99 mol% or more, and particularly preferably 100 mol% as described above. By making the content ratio of the structural unit (I) and the structural unit (II) to be 80 mol% or more in total, patterning characteristics can be ensured when cyclic ketone is used as a developer for a resin film formed of the resin composition. Further, if the content ratio of the structural unit (I) and the structural unit (II) is 80 mol% or more in total, the mechanical strength (tensile strength) of the resin film formed from the resin composition can be improved.
< other structural Unit >
The cyclic olefin polymer may optionally contain structural units (other structural units) other than the structural units (I) and (II). As the other structural unit, for example, a structural unit derived from a known monomer copolymerizable with the monomer capable of forming the structural unit (I) and the monomer capable of forming the structural unit (II) can be used.
Here, when the amount of all the structural units contained in the cyclic olefin polymer is set to 100 mol%, the content of other structural units in the cyclic olefin polymer needs to be 20 mol% or less. Further, the content of other structural units in the cyclic olefin polymer is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 3 mol% or less, still more preferably 1 mol% or less, and particularly preferably 0 mol% from the viewpoint of further improving the patterning characteristics when cyclic ketone is used as a developer.
Property of cyclic olefin polymer
Weight average molecular weight-
The weight average molecular weight (Mw) of the cyclic olefin polymer is preferably 3000 or more, more preferably 5000 or more, further preferably 10000 or more, preferably 500000 or less, more preferably 300000 or less, further preferably 100000 or less. If the weight average molecular weight of the cyclic olefin polymer is 3000 or more, the mechanical strength (tensile strength) of a resin film formed from the resin composition can be improved. Further, if the weight average molecular weight of the cyclic olefin polymer is 500000 or less, the solubility of the resin film formed of the resin composition in cyclic ketone as a developer can be improved. Therefore, the patterning characteristics of the resin film can be further improved when cyclic ketone is used as the developer.
Molecular weight distribution-
The molecular weight distribution (Mw/Mn) of the cyclic olefin polymer is preferably 4.0 or less, more preferably 3.0 or less. If the molecular weight distribution of the cyclic olefin polymer is 4.0 or less, the resolution in patterning the obtained resin film can be improved.
In the present specification, "molecular weight distribution (Mw/Mn)" means a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn). The weight average molecular weight and the number average molecular weight of the cyclic olefin polymer can be obtained as polystyrene conversion values by Gel Permeation Chromatography (GPC).
Synthesis method of Cyclic olefin Polymer
The method for synthesizing the cyclic olefin polymer is not particularly limited, and can be efficiently synthesized by a method including, for example, the steps of: a step of synthesizing a ring-opened polymer by ring-opening polymerization of a norbornene-based monomer, and obtaining a hydrogenated product of the ring-opened polymer by subjecting the obtained ring-opened polymer to hydrogenation (hereinafter referred to as "ring-opening polymerization and hydrogenation step"); and a step of introducing a radical crosslinkable group into the hydrogenated ring-opened polymer by subjecting the hydrogenated ring-opened polymer to a modification reaction (hereinafter referred to as "modification step"). Hereinafter, each step will be described in detail.
[ Ring-opening polymerization and hydrogenation Process ]
In the ring-opening polymerization and hydrogenation step, first, a ring-opening polymer is synthesized by a ring-opening polymerization reaction of the norbornene-based monomer (I) capable of forming the structural unit (I) and the norbornene-based monomer (II) capable of forming the structural unit (II). In addition, a monomer other than the norbornene-based monomer (I) and the norbornene-based monomer (II) may be added as needed to carry out the ring-opening polymerization reaction.
Norbornene monomer (I)
Examples of the norbornene monomer (I) include 2-norbornene-5-methanol and 2-methyl-2-hydroxymethyl bicyclo [2.2.1 ]]Hept-5-ene, 2, 3-dimethylolbicyclo [2.2.1]Hept-5-ene, 3-hydroxy tricyclo [5.2.1.0 2,6 ]Decyl-4, 8-diene, 3-hydroxymethyl tricyclo [5.2.1.0 2,6 ]Dec-4, 8-diene, 4-hydroxytetracyclo [6.2.1.1 3,6 .0 2,7 ]Dodec-9-ene, 4-hydroxymethyl tetracyclo [6.2.1.1 3,6 .0 2,7 ]Dodec-9-ene (common name: tetracyclododecenylmethanol), 4, 5-dimethyloltetracyclo [6.2.1.1 ] 3,6 .0 2,7 ]Dodec-9-ene and the like. The norbornene-based monomer (I) may be used singly or in combination of two or more.
Norbornene-based monomer (II)
Examples of the norbornene monomer (II) include tetracyclo [4.4.0.1 ] 2,5 .1 7,10 ]Dodec-3-ene (common name: tetracyclododecene), 8-ethylene-tetracyclo [4.4.0.1 ] 2,5 .1 7,10 ]Dodec-3-ene (common name: ethylene tetracyclododecene), tricyclo [5.2.1.0 ] 2,6 ]Decyl-3, 8-diene (common name: dicyclopentadiene), 1, 4-alpha-1, 4a,9 a-tetrahydrofluorene (common name: alpha-tetrahydrofluorene), 5-ethylenebicyclo [2.2.1]Hept-2-ene (common name: ethylidene norbornene), bicyclo [2.2.1 ]]Hept-2-ene (also known as "norbornene"), 5-ethyl-bicyclo [2.2.1]Hept-2-ene, 5-butyl-bicyclo [2.2.1]Hept-2-ene, 5-methylene-bicyclo [2.2.1]Hept-2-ene, 5-vinyl-bicyclo [2.2.1]Hept-2-ene, tetracyclo [10.2.1.0 ] 2,11 .0 4,9 ]Pentadec-4,6,8,13-tetraene, 9-methyl-tetracyclo [6.2.1.1 3,6 .0 2,7 ]Dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 3,6 .0 2,7 ]Dodec-4-ene, 9-methylene-tetracyclo [6.2.1.1 3,6 .0 2,7 ]Dodec-4-ene, 9-ethylene-tetracyclo [6.2.1.1 3,6 .0 2,7 ]Dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.1 3,6 .0 2,7 ]Dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 3,6 .0 2,7 ]Dodec-4-ene, pentacyclic [9.2.1.1 3,9 .0 2,10 .0 4,8 ]Pentadeca-5, 12-diene, 9-phenyl-tetracyclo [6.2.1.1 3,6 .0 2,7 ]Dodec-4-ene, tetracyclo [9.2.1.0 ] 2,10 .0 3,8 ]Tetradec-3, 5,7, 12-tetraene, pentacyclo [9.2.1.1 3,9 .0 2,10 .0 4,8 ]Pentadec-12-ene, 5-phenylbicyclo [2.2.1]Hept-2-ene (commonly used name: phenyl norbornene), derivatives thereof, and the like. The derivative means a substance having a substituent in a ring structure. Examples of the substituent that can be contained in the ring structure include an alkyl group, an Alkylene group (alkyl group), a vinyl group, an alkoxycarbonyl group, and an Alkylene group (alkyl group). Furthermore, the ring structure of the derivative may have one or more of these substituents.
The norbornene monomer (II) may be used singly or in combination of two or more.
The ring-opening polymerization reaction can be carried out in a reaction solvent according to a known method.
In this case, the reaction solvent is not particularly limited, and for example, an organic solvent such as tetrahydrofuran or toluene can be used.
Further, as the molecular weight regulator, it is possible to use: ethylene; alpha-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; non-conjugated dienes such as 1, 4-hexadiene, 1, 5-hexadiene, 4-methyl-1, 4-hexadiene, 5-methyl-1, 4-hexadiene, and 1, 7-octadiene, and derivatives thereof, and the like.
As the ring-opening polymerization catalyst, a metal catalyst containing a metal such as molybdenum, tungsten, ruthenium, or the like can be used, and a metal catalyst containing ruthenium is particularly preferable.
Further, the ring-opening polymerization time is usually 1 hour or more and 10 hours or less, preferably 2 hours or more and 5 hours or less. The ring-opening polymerization temperature is usually 20℃or more and 100℃or less, preferably 90℃or less.
Then, the obtained ring-opened polymer is subjected to hydrogenation reaction to synthesize a hydrogenated ring-opened polymer.
In this case, the hydrogenation reaction can be carried out according to a known method. The hydrogenation reaction time, the hydrogenation reaction temperature and the hydrogenation pressure in the hydrogenation reaction are not particularly limited, and the hydrogenation reaction time is usually 1 hour or more and 10 hours or less, preferably 5 hours or less. The hydrogenation reaction temperature is usually 100℃or more and 200℃or less, preferably 180℃or less. The hydrogenation pressure is usually 1MPa to 10MPa, preferably 5 MPa.
[ modification Process ]
In the modification step, a modification reaction with a modifier is performed to introduce a radical crosslinkable group into the hydrogenated ring-opened polymer obtained in the ring-opening polymerization and hydrogenation step, thereby obtaining a cyclic olefin polymer comprising the structural unit (I).
Modifier-
The modifier used for the modification reaction can be appropriately selected according to the structure of the desired radical-crosslinkable group contained in the structural unit (I). In addition, the modifier can be used singly or in combination of plural kinds.
When a radical crosslinkable group having a styrene-based skeleton is introduced, a compound having a functional group (a halogen group, a tosyl group, a methanesulfonyl group, or the like) capable of undergoing a modification reaction with a functional group (a hydroxyl group, or the like) of a hydrogenated ring-opened polymer and a styrene-based skeleton (a styrene-based modifier) can be used as the modifier. Examples of the styrene-based modifier include halogenated methyl styrene such as 2- (fluoromethyl) styrene, 3- (fluoromethyl) styrene, 4- (fluoromethyl) styrene, 2- (chloromethyl) styrene, 3- (chloromethyl) styrene, 4- (chloromethyl) styrene, 2- (bromomethyl) styrene, 3- (bromomethyl) styrene, 4- (bromomethyl) styrene, 2- (iodomethyl) styrene, 3- (iodomethyl) styrene, 4- (iodomethyl) styrene, 2- (tosylmethyl) styrene, 3- (tosylmethyl) styrene, 4- (tosylmethyl) styrene, 2- (methylsulfonylmethyl) styrene, 3- (methylsulfonylmethyl) styrene, and 4- (methylsulfonylmethyl) styrene. These can be used singly or in combination of plural kinds. Among these, from the viewpoint of efficiently carrying out the modification reaction, 4- (chloromethyl) styrene and 4- (bromomethyl) styrene are preferably used.
When a radical crosslinkable group having an acrylate skeleton is introduced, a compound having a functional group (a halogen group, a carboxylic anhydride group, or the like) capable of undergoing a modification reaction with a functional group (a hydroxyl group, or the like) of a hydrogenated ring-opening polymer and an acrylate skeleton (an acrylate-based modifier) can be used as the modifier. Examples of the acrylic acid ester-based modifier include acrylic acid chloride, acrylic acid anhydride, methacrylic acid chloride, and methacrylic acid anhydride. These can be used singly or in combination of plural kinds. Among these, acrylic acid chloride and methacrylic acid chloride are preferably used from the viewpoint of efficiently carrying out the modification reaction.
Procedure and conditions for the modification reaction
The procedure and conditions of the modification reaction are not particularly limited, and may be appropriately set according to the type of modifier used, for example. The reaction solvent used in the modification reaction is not particularly limited, and for example, the same reaction solvent as that used in the ring-opening polymerization reaction can be used.
For example, in the case of using a styrene-based modifier as the modifier, the modification reaction can be performed, for example, by reacting the hydrogenated ring-opened polymer and the styrene-based modifier in a reaction solvent in the presence of a base. In this case, the base is not particularly limited, and may be used: hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide; metal alkoxides such as lithium t-butoxide, sodium t-butoxide, potassium t-butoxide, etc.; organic bases such as triethylamine, pyridine, diazabicycloundecene, diazabicyclononene, and tetramethylguanidine. Among these, from the viewpoint of efficiently carrying out the modification reaction, metal alkoxides such as lithium t-butoxide, sodium t-butoxide, potassium t-butoxide and the like are preferably used.
In the case of using a styrene-based modifier as the modifier, a compound capable of becoming a source of generation of iodide ions, such as potassium iodide and tetrabutylammonium iodide, is preferably used as the catalyst. By incorporating this catalyst, the reaction in the modification step can be promoted. The mixing ratio of the catalyst capable of generating iodide ions may be, for example, 1.0 part by mass or more and 10.0 parts by mass or less per 100 parts by mass of the hydrogenated ring-opened polymer.
When a styrene-based modifier is used as the modifier, the modification reaction temperature and the modification reaction time are not particularly limited, and the modification reaction temperature is usually from-10 ℃ to 100 ℃ and the modification reaction time is usually from 1 hour to 15 hours.
In addition, for example, when an acrylic acid ester-based modifier is used as the modifier, the modification reaction can be performed by reacting the hydrogenated ring-opened polymer and the acrylic acid ester-based modifier in a reaction solvent in the presence of a modification reaction catalyst. In this case, the modification reaction catalyst is not particularly limited, and for example, triethylamine, pyridine, and the like can be used. In the case of using an acrylic acid ester-based modifier as the modifier, the modification reaction temperature and the modification reaction time are not particularly limited, and the modification reaction temperature is usually from-10 ℃ to 15 ℃ and the modification reaction time is usually from 1 hour to 15 hours.
< radical initiator >
The radical initiator is a component capable of generating radicals by exposure and heating to react radical crosslinkable groups and crosslink the cyclic olefin polymer when the resin composition is used to obtain a resin film.
Here, as the radical initiator, for example, a photo radical initiator, a thermal radical initiator, or the like can be used. In addition, the radical initiator can be used singly or in combination of plural kinds. Further, as the radical initiator, a photo radical initiator is preferably used.
Photo radical initiator
As the photo-radical initiator, an acyl phosphine oxide-based, oxime ester-based, or aromatic ketone-based photo-radical initiator or the like can be used. The photo radical initiator can be used singly or in combination of plural kinds. In view of further improving the exposure sensitivity and improving the film residue ratio after development, an oxime ester type photo radical initiator is particularly preferably used as the photo radical initiator.
Examples of the acyl phosphine oxide-based photo-radical initiator include bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, and 2,4, 6-trimethylbenzoyl phenyl ethoxy phosphine oxide.
As the oxime ester-based photo radical initiator, for example, can be used: 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime) (manufactured by Basoff corporation, commercially available as "Irgacure (registered trademark) OXE 01"); 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime) (manufactured by Basoff company, commercially available as "Irgacure OXE 02"); and a commercially available compound (chemical formula not disclosed) manufactured by basf as "Irgacure OXE 03".
Further, as the aromatic ketone-based photo radical initiator, benzophenone, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-dimethoxy-1, 2-diphenylethan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [ 4-methylthio ] phenyl ] -2-morpholinopropane-1-one, methyl o-benzoylbenzoate, [4- (methylthiothio) phenyl ] phenyl methane, 1, 4-dibenzoyl benzene, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, benzil, and the like can be used.
Content of radical initiator
The content of the radical initiator in the resin composition of the present invention is preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, further preferably 5 parts by mass or more, preferably 25 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, based on 100 parts by mass of the cyclic olefin polymer. If the content of the radical initiator in the resin composition is 0.3 parts by mass or more with respect to 100 parts by mass of the cyclic olefin polymer, the patterning characteristics can be sufficiently improved when cyclic ketone is used as a developer for a resin film formed from the resin composition. On the other hand, if the content of the radical initiator in the resin composition is 25 parts by mass or less relative to 100 parts by mass of the cyclic olefin polymer, the value of the dielectric loss tangent of the resin film formed from the resin composition can be reduced.
< crosslinking agent having at least two polymerizable unsaturated bonds >
From the viewpoint of reducing the dielectric loss tangent of the obtained resin film and improving the stretchability, the resin composition of the present invention preferably contains a crosslinking agent having at least two polymerizable unsaturated bonds.
The crosslinking agent is a component capable of forming a strong crosslinked structure in the resin film together with the cyclic olefin polymer by reacting with the cyclic olefin polymer through a radical reaction induced by the radical initiator when the resin composition is used to obtain the resin film.
The crosslinking agent is not particularly limited as long as it has two or more polymerizable unsaturated bonds, and any crosslinking agent can be used. In addition, the crosslinking agent can be used singly or in combination of plural kinds.
Examples of the crosslinking agent include a crosslinking agent having a (meth) acryloyl group, a crosslinking agent having a styryl group, and a crosslinking agent having an allyl group.
In addition, in the present specification, "(meth) acryl" means acryl and/or methacryl.
Examples of the crosslinking agent having a (meth) acryloyl group include 1, 6-hexanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris (2-acryloyloxyethyl) isocyanurate, bisphenol A dimethacrylate, polybutadiene terminal diacrylate (manufactured by Osaka organic chemical Co., ltd., "BAC-45"), polyphenylene ether having a methacryloyl group (manufactured by SABIC Co., ltd., "NORYL (registered trademark) SA 9000"), and the like.
Examples of the crosslinking agent having a styrene group include a crosslinking agent (IV) exemplified by 1, 2-divinylbenzene, 1, 3-divinylbenzene, 1, 4-divinylbenzene, and 1, 4-diisopropenylbenzene "OPE-2St 1200" and "OPE-2St 2200" (both manufactured by Mitsubishi gas chemical Co., ltd.).
Examples of the crosslinking agent having an allyl group include diallyl ether, tetraallyloxyethane, pentaerythritol triallyl ether, 9-bis (4-allyloxyphenyl) fluorene, diallyl adipate, triallyl 1,3, 5-trimesic acid, triallyl cyanurate, diallyl propyl isocyanurate, triallyl isocyanurate (crosslinking agent (III). Hereinafter, may be abbreviated as "TAIC"), 2,4, 6-trimethyl-2, 4, 6-trivinylcyclotrisiloxane, and the like.
Further, as the crosslinking agent, a crosslinking agent (III) represented by the following formula (III) and a crosslinking agent (IV) represented by the following formula (IV) are preferable from the viewpoint of further reducing the dielectric loss tangent of a resin film formed from the resin composition and further improving the stretchability.
[ chemical formula 9]
[ chemical formula 10]
In the crosslinking agent (IV), A is a divalent organic group. Here, as the divalent organic group constituting a of the formula (IV), an organic group represented by the following formula (VII) is preferable.
[ chemical formula 11]
In the formula (VII), R a 、R b 、R c 、R d 、R e 、R f 、R g R is as follows h Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
As R capable of being represented by formula (VII) a ～R h Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As R capable of being represented by formula (VII) a ～R h The alkyl group having 1 to 6 carbon atoms is not particularly limited, and is preferably a methyl group or an ethyl group, more preferably a methyl group.
In the crosslinking agent (IV), a and b are each independently an integer of 0 to 300. But does not include the case where one of a and b is 0. From the viewpoint of further reducing the dielectric loss tangent of a resin film formed from the resin composition and further improving the stretchability, a and b are each preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and even more preferably an integer of 1 to 10.
Further, the number average molecular weight of the crosslinking agent (IV) is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more, particularly preferably 1000 or more, preferably 3000 or less, more preferably 2500 or less, from the viewpoint of further reducing the dielectric loss tangent of the resin film formed from the resin composition and further improving the stretchability.
Content of crosslinker
The content of the crosslinking agent in the resin composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, particularly preferably 30 parts by mass or more, preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, still more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less, relative to 100 parts by mass of the cyclic olefin polymer. If the content of the crosslinking agent in the resin composition is 5 parts by mass or more relative to 100 parts by mass of the cyclic olefin polymer, the dielectric loss tangent of a resin film formed from the resin composition can be reduced and the stretchability can be improved. On the other hand, if the content of the crosslinking agent in the resin composition is 100 parts by mass or less relative to 100 parts by mass of the cyclic olefin polymer, patterning characteristics can be sufficiently ensured when cyclic ketone is used as the developer for the resin film formed from the resin composition.
Combination of crosslinking agents
Further, from the viewpoint of reducing the dielectric loss tangent of a resin film formed from the resin composition and improving the stretchability, the resin composition preferably contains both the crosslinking agent (III) and the crosslinking agent (IV).
When the resin composition contains both the crosslinking agent (III) and the crosslinking agent (IV), the content of the crosslinking agent (III) in the resin composition is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, preferably 60 mass% or less, still more preferably 50 mass% or less, and still more preferably 40 mass% or less, based on 100 mass% of the total of the content of the crosslinking agent (III) and the content of the crosslinking agent (IV). If the content of the crosslinking agent (III) is within the above range in the total content of the crosslinking agent (III) and the crosslinking agent (IV), the dielectric loss tangent of the resin film formed from the resin composition can be reduced and the stretchability can be improved.
< solvent >
The solvent that can be optionally contained in the resin composition of the present invention is not particularly limited, and examples thereof include: aromatic solvents such as toluene, o-xylene, m-xylene, p-xylene, 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, and tetralin; hydrocarbon solvents such as cyclohexane and decalin; ether solvents such as dibutyl ether, diisoamyl ether, tetrahydrofuran, cyclopentylmethyl ether, anisole, and the like; ester solvents such as butyl acetate, hexyl acetate, propylene glycol monomethyl ether acetate, and the like; ketone solvents such as methyl ethyl ketone, diisobutyl ketone, and cyclopentanone. These solvents can be used singly or in combination of plural kinds.
Further, the content of the solvent in the resin composition is preferably the following amount: the total amount of the solvents is preferably 10 mass% or more, more preferably 20 mass% or more, preferably 60 mass% or less, more preferably 50 mass% or less, based on the total mass of the resin composition.
< additive component >
The optional additive components that can be contained in the resin composition of the present invention are not particularly limited, and examples thereof include surfactants, antioxidants, sensitizers, adhesion promoters, and the like. These additional components can be used singly or in combination of two or more. From the viewpoints of improving the coatability of the resin composition of the present invention and improving the uniformity of the film thickness of the obtained resin film, it is particularly preferable to contain a surfactant as an additive component.
The surfactant is not particularly limited, and a known silicone surfactant, fluorine surfactant, or the like can be used. The content of the surfactant in the resin composition is preferably 0.1 mass% or less, more preferably 0.05 mass% or less, based on the total mass of the resin composition.
< method for producing resin composition >
The resin composition of the present invention can be prepared by mixing the above-described essential components and various optional components by a known method. The resin composition of the present invention is used in the form of, for example, a resin composition obtained by dissolving each component in a solvent and filtering the solution. For dissolution in the solvent, a known mixer such as a stirrer, a ball mill, a sand mill, a bead mill, a pigment dispersing machine, a kneader, an ultrasonic dispersing machine, a homogenizer, a planetary mixer, or a palmix can be used. In addition, in the case of filtering, a usual filtering method using a filter material such as a filter can be used.
< method for producing resin film >
In addition, the resin composition of the present invention can be formed into a resin film by using a known film forming method (refer to, for example, international publication No. 2015/033901). The resin film thus obtained is not particularly limited, and a resin film having a desired pattern can be formed by performing an exposure step and a development step of irradiating an arbitrary active energy ray, for example, exposure light having a wavelength of 200nm or more and 500nm or less.
In particular, the resin film formed from the resin composition of the present invention can efficiently form a desired pattern even when cyclic ketones such as cyclopentanone and cyclohexanone are used as a developer in a developing step.
The pre-baking (prebake) step may be performed before the exposure step, or the post-exposure baking (PEB) step may be performed at a desired timing after the exposure step is started, as necessary. Further, if necessary, a post baking step may be performed after the end of the developing step.
Examples
The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "%" and "parts" indicating amounts are based on mass.
In examples and comparative examples, measurement of various properties and various evaluations were performed by the following methods, respectively.
< weight average molecular weight and molecular weight distribution >
The cyclic olefin polymers obtained in examples and comparative examples were measured for weight average molecular weight (Mw) and number average molecular weight (Mn) by gel permeation chromatography, and the molecular weight distribution (Mw/Mn) was calculated.
Specifically, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cyclic olefin polymer were determined as standard polystyrene conversion values using a gel permeation chromatograph (HLC-8220, manufactured by Tosoh Co., ltd.) and tetrahydrofuran as an eluent. Then, the molecular weight distribution (Mw/Mn) was calculated.
< stretchability (tensile elongation) and mechanical Strength (tensile Strength) >
The resin compositions prepared in each example and each comparative example were spin-coated on a 4-inch silicon wafer on which an aluminum film having a film thickness of 50nm was formed using a sputtering apparatus (manufactured by Zhimau electronics, inc., i-Miller CFS-4 EP-LL), and then baked at 90℃for 2 minutes using a heating plate to form a resin film formed from the resin composition. 1000mJ/cm Using a mask aligner 2 After exposure to light, the resin film was cured by heating at 230℃for 1 hour in nitrogen, to obtain a 10 μm thick silicon wafer with a resin film. The obtained silicon wafer with the resin film was immersed in a 0.1 mol% aqueous hydrochloric acid solution for 12 hours, and aluminum was etched to peel the resin film from the silicon wafer with the resin film, followed by drying in an oven at 110 ℃ for 1 hour.
The dried resin film was cut into a rectangular shape having a width of 5mm and a length of 40mm to obtain a test piece, and the test piece was subjected to a tensile test. Specifically, a tensile test was performed at 23℃with a clamp spacing of 20mm and a tensile speed of 2 mm/min by a tensile tester (manufactured by Shimadzu corporation, "AGS-10 kNX"), and elongation and strength at the breaking point were measured. Eight test pieces were tested, and the average value of the highest three points was used as the tensile elongation and tensile strength of the resin films formed using the resin compositions obtained in each example and each comparative example, and evaluated according to the following criteria. The larger the value of the tensile elongation, the higher the stretchability of the resin film. Further, the higher the stretchability of the resin film, the less likely to cause cracking or peeling in the temperature cycle test or the drop impact test, and therefore, the higher the stretchability is preferred. Further, the greater the tensile strength means the higher the mechanical strength of the resin film.
Stretch >
A: a tensile elongation of 10% or more
B: a tensile elongation of 5% or more and less than 10%
C: tensile elongation of less than 5%
Mechanical Strength
A: tensile strength of 70MPa or more
B: tensile strength of 60MPa or more and less than 70MPa
C: tensile strength of less than 60MPa
< dielectric loss tangent >
The resin compositions prepared in each example and each comparative example were spin-coated on a 4-inch silicon wafer on which an aluminum film having a film thickness of 50nm was formed using a sputtering apparatus (manufactured by Zhimau electronics, inc., i-Miller CFS-4 EP-LL), and then baked at 90℃for 2 minutes using a heating plate to form a resin film formed from the resin composition. Then, using a mask aligner (made by Canon Co., ltd., "PLA 501F"), a mixed ray of g-h-i was used at 1000mJ/cm 2 After exposure to the irradiation amount of (2), the resin film was cured by heating at 180℃for 1 hour in nitrogen, to obtain a 10 μm thick silicon wafer with a resin film. The obtained silicon wafer with the resin film was immersed in a 0.1 mol% aqueous hydrochloric acid solution for 12 hours, and aluminum was etched, whereby the resin film was peeled from the silicon wafer. After drying in an oven at 110℃for 1 hour, the test piece was cut into a rectangular shape having a width of 2mm and a length of 50mm, and the dielectric loss tangent of 10GHz was measured on the test piece by a cavity resonator method.
A: dielectric loss tangent of less than 0.0035
B: dielectric loss tangent of 0.0035 or more and less than 0.0040
C: dielectric loss tangent of 0.0040 or more
< presence or absence of turbidity >
After spin-coating the resin compositions prepared in each example and each comparative example on a 4-inch silicon wafer, a resin film formed of the resin composition was formed by pre-baking at 90 ℃ for 2 minutes using a heating plate. The obtained resin film was visually observed to confirm the presence or absence of turbidity.
< patterning Property >
After spin-coating the resin compositions prepared in each example and each comparative example on a 4-inch silicon wafer, a resin film formed of the resin composition was formed by pre-baking at 90 ℃ for 2 minutes using a heating plate. Then, using a g-h-i mixed ray with a mask aligner (made by Canon corporation, "PLA 501F"), the mask having a hole pattern with a diameter of 100 μm was used at a rate of 700mJ/cm 2 After exposure to the irradiation amount of (2), the resulting film was immersed in cyclopentanone for 90 seconds and developed. The presence or absence of the opening in the hole pattern was confirmed with an optical microscope for the developed resin film.
Example 1
< Synthesis of Cyclic olefin Polymer (B-1) >
Ring-opening polymerization and hydrogenation Process ]
100 parts of a monomer mixture composed of 15 mol% of 2-norbornene-5-methanol (hereinafter abbreviated as "NBMOH") as the norbornene-based monomer (I) and 85 mol% of methylene-bridged tetrahydrofluorene (hereinafter abbreviated as "MTF") as the norbornene-based monomer (II), 1.0 parts of 1, 5-hexadiene as a molecular weight regulator, 0.025 parts of (1, 3-bis-trimethylphenyl imidazolin-2-ylidene) (tricyclohexylphosphine) benzylidenedichloride (synthesized by the method described in Org. Lett., volume 1, page 953, 1999) as the ring-opening polymerization catalyst, and 300 parts of tetrahydrofuran as a reaction solvent were charged into a nitrogen-substituted glass pressure reactor, and reacted at 80℃for 4 hours while stirring to obtain a polymerization reaction solution.
The resulting polymerization reaction solution was charged into an autoclave, and after stirring at 150℃and a hydrogen pressure of 4MPa for 5 hours, 300 parts of tetrahydrofuran as a reaction solvent was added to the reaction solution. These were added dropwise to 8000 parts of methanol, and the resultant precipitate was recovered by filtration and dried under reduced pressure at 50℃to thereby obtain a hydrogenated ring-opened polymer (A-1).
< modification Process >
A three-necked flask equipped with a stirring blade and a thermometer was subjected to nitrogen substitution, and 100 parts of hydrogenated ring-opened polymer (A-1), 87.4 parts of triethylamine as a catalyst for the modification reaction, and 500 parts of tetrahydrofuran as a reaction solvent were added thereto, and the reaction solution was cooled to 0℃with an ice bath. While maintaining the temperature of the reaction solution at 10℃or lower, 54.2 parts of methacryloyl chloride as a modifier was added dropwise, and the mixture was stirred for 2 hours. Further, the reaction solution was warmed to room temperature and stirred for a further 12 hours. Next, 200 parts of tetrahydrofuran as a reaction solvent was added to the reaction solution, and then the solution was cooled to 0 ℃, and 50 parts of methanol based on 100 parts of methacryloyl chloride was added to the solution while keeping the temperature of the reaction solution at 10 ℃ or lower, and the solution was stirred at 0 ℃ for 1 hour, and then the solution was warmed to room temperature and stirred for 1 hour.
The reaction solution was added dropwise to 8000 parts of methanol, and the resultant precipitate was recovered by filtration. The precipitate was washed three times with methanol and then dried under reduced pressure at 50℃to thereby obtain a cyclic olefin polymer (B-1) as a modified product of a hydrogenated ring-opened polymer (refer to the following formula). The weight average molecular weight of the cyclic olefin polymer (B-1) was 20100 and the molecular weight distribution was 2.13 as determined by GPC.
By passing through 1 The H-NMR measurement revealed that the modification ratio of the methacryloyl groups of the hydrogenated ring-opened polymer (A-1) was 100%, and the content of structural units derived from the methacryloyl group-modified NBMOH in the cyclic olefin polymer (B-1) was 15 mol%.
[ chemical formula 12]
< preparation of resin composition >
100 parts of the cyclic olefin polymer (B-1) obtained as described above, 5 parts of "Irgacure OEX01" (manufactured by Basoff Co.) as a radical initiator, and anisole (solvent) in an amount of 30% in total with respect to the total mass of the resin composition were mixed and dissolved. Then, KP-341 (made by Silicones) was added as a surfactant so as to be 0.03% of the total mass of the resin composition, and the mixture was filtered through a polytetrafluoroethylene filter having a pore size of 0.45. Mu.m, to prepare a resin composition.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 1.
Example 2
A resin composition was prepared in the same manner as in example 1, except that the cyclic olefin polymer (B-2) prepared as follows was used instead of the cyclic olefin polymer (B-1) in preparing the resin composition.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 1.
< Synthesis of Cyclic olefin Polymer (B-2) ]
Ring-opening polymerization and hydrogenation Process ]
The same operation as in example 1 was performed except that NBMOH was changed to tetracyclododecenylmethanol (hereinafter abbreviated as "TCDMOH") and tetrahydrofuran was changed to toluene, to obtain a hydrogenated ring-opened polymer (A-2).
< modification procedure >
The same operation as in example 1 was performed except that the hydrogenated ring-opened polymer (A-1) was changed to hydrogenated ring-opened polymer (A-2), the amount of triethylamine was changed to 83.5 parts, the amount of methacryloyl chloride was changed to 51.3 parts, and tetrahydrofuran was changed to toluene, to obtain a cyclic olefin polymer (B-2) as a modified product of hydrogenated ring-opened polymer (see the following formula). The weight average molecular weight of the cyclic olefin polymer (B-2) was 22900 and the molecular weight distribution was 2.03 as determined by GPC.
By passing through 1 The H-NMR measurement revealed that the modification ratio of the methacryloyl groups of the hydrogenated ring-opened polymer (A-2) was 100%, and the content of structural units derived from the TCDMOH after the modification of the methacryloyl groups in the cyclic olefin polymer (B-2) was 15 mol%.
[ chemical formula 13]
Example 3
A cyclic olefin polymer (B-1) and a resin composition were produced in the same manner as in example 1 except that 25 parts of "OPE-2St 1200" (number average molecular weight: 1200, structure of the following formula (VIII)) as a crosslinking agent (IV) was added to prepare a resin composition.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 1.
[ chemical formula 14]
Example 4
A resin composition was prepared in the same manner as in example 1 except that the cyclic olefin polymer (B-3) prepared as follows was used in place of the cyclic olefin polymer (B-1), and 50 parts of "OPE-2St 2200" (number average molecular weight: 2200, manufactured by Mitsubishi gas chemical Co., ltd.) as a crosslinking agent (IV) was added to prepare the resin composition.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 1.
< Synthesis of Cyclic olefin Polymer (B-3) ]
Ring-opening polymerization and hydrogenation Process ]
The same operation as in example 1 was conducted except that the MTF was changed to 55 mol% and 30 mol% of phenylnorbornene was added, to obtain a hydrogenated ring-opened polymer (A-3).
< modification procedure >
The same operation as in example 1 was conducted except that the hydrogenated ring-opened polymer (A-1) was changed to hydrogenated ring-opened polymer (A-3), the amount of triethylamine was changed to 91.9 parts, and the amount of methacryloyl chloride was changed to 55.3 parts, to obtain a cyclic olefin polymer (B-3) as a modified product of the hydrogenated ring-opened polymer (see the following formula). The weight average molecular weight of the cyclic olefin polymer (B-3) was 16400 and the molecular weight distribution was 1.59 as determined by GPC.
By passing through 1 The H-NMR measurement revealed that the modification ratio of the methacryloyl groups of the hydrogenated ring-opened polymer (A-3) was 100%, and the content of structural units derived from the methacryloyl group-modified NBMOH in the cyclic olefin polymer (B-3) was 15 mol%.
[ chemical formula 15]
Example 5
A cyclic olefin polymer (B-1) and a resin composition were produced in the same manner as in example 1 except that 20 parts of a crosslinking agent (III) (TAIC, new Shitsu Co., ltd.) was added to prepare the resin composition.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 1.
Example 6
A cyclic olefin polymer (B-2) and a resin composition were produced in the same manner as in example 2 except that 10 parts of a crosslinking agent (III) (TAIC, new Shitsu Co., ltd.) and 25 parts of "OPE-2St 1200" (number average molecular weight: 1200, structure of the above formula (VIII) were added as the crosslinking agent (IV) in the preparation of the resin composition.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 1.
Example 7
A cyclic olefin polymer (B-1) and a resin composition were produced in the same manner as in example 1 except that 10 parts of a crosslinking agent (III) (TAIC, new Shitsu Co., ltd.) and 50 parts of "OPE-2St 1200" (number average molecular weight: 1200, structure of the above formula (VIII) were added as the crosslinking agent (IV) in the preparation of the resin composition.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 1.
Example 8
A cyclic olefin polymer (B-2) and a resin composition were produced in the same manner as in example 2 except that 10 parts of a crosslinking agent (III) (TAIC, new Shitsu Co., ltd.) and 25 parts of "OPE-2St 2200" (number average molecular weight: 2200, manufactured by Mitsubishi gas chemical Co., ltd.) as a crosslinking agent (IV) were added to prepare a resin composition.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 2.
Example 9
A resin composition was prepared in the same manner as in example 6, except that the cyclic olefin polymer (B-4) prepared as follows was used instead of the cyclic olefin polymer (B-2) in preparing the resin composition.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 2.
< Synthesis of Cyclic olefin Polymer (B-4) >
Ring-opening polymerization and hydrogenation Process ]
The same operation as in example 1 was conducted except that NBMOH was changed to 50 mol% and MTF was changed to 50 mol%, to obtain a hydrogenated ring-opened polymer (A-4).
< modification procedure >
The same operation as in example 1 was conducted except that the hydrogenated ring-opened polymer (A-1) was changed to hydrogenated ring-opened polymer (A-4), the amount of triethylamine was changed to 355.5 parts, and the amount of methacryloyl chloride was changed to 204.2 parts, to obtain a cyclic olefin polymer (B-4) as a modified product of the hydrogenated ring-opened polymer (see the following formula). The weight average molecular weight of the cyclic olefin polymer (B-4) was 22000 and the molecular weight distribution was 2.14 as determined by GPC.
By passing through 1 The H-NMR measurement confirmed that the methacryloyl modification ratio of the hydrogenated ring-opened polymer (A-4) was 100% and the content of structural units derived from the methacryloyl-modified NBMOH in the cyclic olefin polymer (B-4) was 50 mol%.
[ chemical formula 16]
Comparative example 1
In the production of the resin composition, a resin composition was produced in the same manner as in example 1, except that the cyclic olefin polymer (B-5) produced as follows was used in place of the cyclic olefin polymer (B-1), and 50 parts of "OPE-2St 1200" (number average molecular weight: 1200, produced by Mitsubishi gas chemical Co., ltd.) as a crosslinking agent (IV) was added, and tetralin was used in place of anisole.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 2.
< Synthesis of Cyclic olefin Polymer (B-5) >
Ring-opening polymerization and hydrogenation Process ]
The same operation as in example 1 was conducted except that the MTF was changed to 55 mol% and 30 mol% of ethylene tetracyclododecene (hereinafter abbreviated as "ETD") was added, to obtain a hydrogenated ring-opened polymer (A-5).
< modification procedure >
The same operation as in example 1 was conducted except that the hydrogenated ring-opened polymer (A-1) was changed to hydrogenated ring-opened polymer (A-5), the amount of triethylamine was changed to 355.5 parts, and the amount of methacryloyl chloride was changed to 204.2 parts, to obtain a cyclic olefin polymer (B-5) as a modified product of the hydrogenated ring-opened polymer (see the following formula). The weight average molecular weight of the cyclic olefin polymer (B-5) was 20000 and the molecular weight distribution was 1.76 as measured by GPC.
By passing through 1 The H-NMR measurement revealed that the modification ratio of the methacryloyl groups of the hydrogenated ring-opened polymer (A-5) was 100%, and the content of structural units derived from the methacryloyl-modified NBMOH in the cyclic olefin polymer (B-5) was 15 mol%.
[ chemical formula 17]
Comparative example 2
In the same manner as in example 1 except that the cyclic olefin polymer (B-6) prepared as follows was used in place of the cyclic olefin polymer (B-1) and tetralin was used in place of anisole in the preparation of the resin composition, a resin composition was prepared.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 2.
< Synthesis of Cyclic olefin Polymer (B-6) >
Ring-opening polymerization and hydrogenation Process ]
The same procedure as in example 1 was repeated except that the MTF was changed to ETD in example 1 to obtain a hydrogenated ring-opened polymer (A-6).
< modification procedure >
The same operation as in example 1 was conducted except that the hydrogenated ring-opened polymer (A-1) was changed to hydrogenated ring-opened polymer (A-6), the amount of triethylamine was changed to 94.5 parts, and the amount of methacryloyl chloride was changed to 53.8 parts, to obtain a cyclic olefin polymer (B-6) as a modified product of the hydrogenated ring-opened polymer (see the following formula). The weight average molecular weight of the cyclic olefin polymer (B-6) was 17700 and the molecular weight distribution was 2.62 as determined by GPC.
By passing through 1 The H-NMR measurement revealed that the modification ratio of the methacryloyl groups of the hydrogenated ring-opened polymer (A-6) was 100%, and the content of structural units derived from the methacryloyl groups-modified NBMOH in the cyclic olefin polymer (B-6) was 15 mol%.
[ chemical formula 18]
Comparative example 3
In the same manner as in example 1 except that the cyclic olefin polymer (B-7) as a modified addition polymer prepared as described below was used in place of the cyclic olefin polymer (B-1) and tetralin was used in place of anisole in the preparation of the resin composition, a resin composition was prepared.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 2.
< Synthesis of Cyclic olefin Polymer (B-7) ]
Addition polymerization Process
The addition polymer (A-7) of norbornene and NBMOH was synthesized according to the method described in macromolecules29,2761 (1996) except that the test scale (scale) was 20 times.
< modification procedure >
The same operation as in example 1 was conducted except that the hydrogenated ring-opening polymer (A-1) was changed to the addition polymer (A-7), the amount of triethylamine was changed to 170.4 parts, and the amount of methacryloyl chloride was changed to 95.3 parts, to obtain a cyclic olefin polymer (B-7) as a modified addition polymer (see the following formula). The weight average molecular weight of the cyclic olefin polymer (B-7) was 28100 and the molecular weight distribution was 1.84 as determined by GPC.
By passing through 1 The H-NMR measurement confirmed that the modification ratio of the methacryloyl group of the addition polymer (A-7) was 100% and the content of structural units derived from the methacryloyl group-modified NBMOH in the cyclic olefin polymer (B-7) was 15 mol%.
[ chemical formula 19]
Comparative example 4
A cyclic olefin polymer (B-7) was produced in the same manner as in comparative example 3. Then, in the preparation of a resin composition, a resin composition was prepared in the same manner as in example 1, except that the cyclic olefin polymer (B-7) was used in place of the cyclic olefin polymer (B-1), and 50 parts of "OPE-2St 1200" (number average molecular weight: 1200, obtained by Mitsubishi gas chemical Co., ltd., having the structure of the above formula (VIII)) was added as a crosslinking agent (IV), and tetralin was used in place of anisole.
Then, various evaluations were performed as described above using the obtained resin composition. The results are shown in Table 2.
TABLE 1
TABLE 2
As is clear from tables 1 to 2, the resin compositions of examples 1 to 9 contain a cyclic olefin polymer containing the structural unit (I) and the structural unit (II) in a total amount of 80 mol% or more and a radical initiator, and if the resin compositions of examples 1 to 9 are used, a resin film having excellent patterning characteristics when cyclic ketone is used as a developer can be formed.
Industrial applicability
According to the resin composition comprising a cyclic olefin polymer of the present invention, a resin film excellent in patterning characteristics when a cyclic ketone is used as a developer can be formed.
Claims (5)
1. A resin composition comprising a cyclic olefin polymer and a radical initiator,
the cyclic olefin polymer comprises a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II), wherein when the total amount of the structural units contained in the cyclic olefin polymer is 100 mol%, the total of the content of the structural unit (I) and the content of the structural unit (II) in the cyclic olefin polymer is 80 mol% or more,
in the formula (I), R 1 ～R 4 At least one of them is a radical crosslinkable group,
r not being a radical-crosslinkable group 1 ～R 4 R is independently a hydrogen atom, an alkyl group or an aromatic ring group, and is not a radical crosslinkable group 1 ～R 4 Two of which can together formThe ring is provided with a plurality of grooves,
m is an integer of 0 to 4,
in the formula (II), R 5 ～R 8 At least one of them is an aromatic ring group, or R 5 ～R 8 Together forming an aromatic ring-containing structure,
r not belonging to aromatic ring groups and not forming aromatic ring-containing structure 5 ～R 8 Each independently is a hydrogen atom or an alkyl group,
n is an integer of 0 to 4 inclusive.
2. The resin composition according to claim 1, wherein the content of the structural unit (II) in the cyclic olefin polymer is 70 mol% or more, based on 100 mol% of the total structural units contained in the cyclic olefin polymer.
3. The resin composition according to claim 1, wherein the radical crosslinkable group has at least one of a styrene-based skeleton and an acrylate skeleton.
4. The resin composition according to any one of claims 1 to 3, wherein the resin composition further comprises a crosslinking agent having at least two polymerizable unsaturated bonds.
5. The resin composition according to claim 4, wherein the crosslinking agent comprises at least one of a crosslinking agent (III) represented by the following formula (III) and a crosslinking agent (IV) represented by the following formula (IV),
in the formula (IV), a is a divalent organic group, a and b are integers of 0 to 300, and a and b may be the same or different, but are not limited to the case where only one of a and b is 0.
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| PCT/JP2022/034479 WO2023053976A1 (en) | 2021-09-29 | 2022-09-14 | Resin composition |
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| JP2013203892A (en) * | 2012-03-28 | 2013-10-07 | Nippon Zeon Co Ltd | Polymerizable composition, crosslinkable resin molding, crosslinked resin molding and laminate |
| WO2016031766A1 (en) * | 2014-08-26 | 2016-03-03 | 日本ゼオン株式会社 | Crosslinkable resin molded body, crosslinked resin molded body and laminate |
| TW201612200A (en) * | 2014-08-26 | 2016-04-01 | Zeon Corp | Crosslinkable resin molded body, crosslinked resin molded body and laminate |
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