WO2021117762A1 - 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 - Google Patents
樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 Download PDFInfo
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- WO2021117762A1 WO2021117762A1 PCT/JP2020/045841 JP2020045841W WO2021117762A1 WO 2021117762 A1 WO2021117762 A1 WO 2021117762A1 JP 2020045841 W JP2020045841 W JP 2020045841W WO 2021117762 A1 WO2021117762 A1 WO 2021117762A1
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- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KJPLRQFMMRYYFL-UHFFFAOYSA-N naphthalen-2-yl cyanate Chemical compound C1=CC=CC2=CC(OC#N)=CC=C21 KJPLRQFMMRYYFL-UHFFFAOYSA-N 0.000 description 1
- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 0.000 description 1
- KVQQRFDIKYXJTJ-UHFFFAOYSA-N naphthalene-1,2,3-tricarboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(C(O)=O)C(C(=O)O)=CC2=C1 KVQQRFDIKYXJTJ-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002866 paraformaldehyde Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- NOHFYJWXIIYRIP-UHFFFAOYSA-N phenyl 4-cyanatobenzoate Chemical compound C=1C=C(OC#N)C=CC=1C(=O)OC1=CC=CC=C1 NOHFYJWXIIYRIP-UHFFFAOYSA-N 0.000 description 1
- CWHFDTWZHFRTAB-UHFFFAOYSA-N phenyl cyanate Chemical compound N#COC1=CC=CC=C1 CWHFDTWZHFRTAB-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical class [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- JSSXHAMIXJGYCS-UHFFFAOYSA-N piperazin-4-ium-2-carboxylate Chemical compound OC(=O)C1CNCCN1 JSSXHAMIXJGYCS-UHFFFAOYSA-N 0.000 description 1
- SMCWNPAVVQIDBM-UHFFFAOYSA-N piperidine-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCN1C(O)=O SMCWNPAVVQIDBM-UHFFFAOYSA-N 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- MHRLWUPLSHYLOK-UHFFFAOYSA-N thiomorpholine-3,5-dicarboxylic acid Chemical compound OC(=O)C1CSCC(C(O)=O)N1 MHRLWUPLSHYLOK-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004360 trifluorophenyl group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- RKLXSINPXIQKIB-UHFFFAOYSA-N trimethoxy(oct-7-enyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCC=C RKLXSINPXIQKIB-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- XQEGZYAXBCFSBS-UHFFFAOYSA-N trimethoxy-(4-methylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=C(C)C=C1 XQEGZYAXBCFSBS-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QYJYJTDXBIYRHH-UHFFFAOYSA-N trimethoxy-[8-(oxiran-2-ylmethoxy)octyl]silane Chemical compound C(C1CO1)OCCCCCCCC[Si](OC)(OC)OC QYJYJTDXBIYRHH-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08F234/00—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
- H05K1/0298—Multilayer circuits
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Definitions
- the present invention relates to a resin composition, a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device.
- the insulating layer is also required to be thinned, and a resin sheet containing no glass cloth is required.
- Thermosetting resin is the mainstream of the resin composition used as the material of the insulating layer, and drilling for obtaining continuity between the insulating layers is generally performed by laser processing.
- an exposure method a method of exposing through a photomask using a mercury lamp as a light source is used, and a material that can be suitably exposed by the light source of this mercury lamp is required.
- a ghi mixed line g-line wavelength 436 nm, h-line wavelength 405 nm, i-line wavelength 365 nm
- a general-purpose photocuring initiator can be selected. ..
- a direct drawing exposure method for directly drawing on a photosensitive resin composition layer based on digital data of a pattern without using a photomask has been introduced.
- This direct drawing exposure method has better alignment accuracy than the exposure method using a photomask and can obtain a high-definition pattern. Therefore, it is particularly introduced in a substrate that requires high-density wiring formation. I'm out.
- the light source uses monochromatic light such as a laser, and among them, a light source having a wavelength of 405 nm (h line) is used in a DMD (Digital Micromirror Device) type device capable of forming a high-definition resist pattern.
- DMD Digital Micromirror Device
- Alkaline development is used as the development method because a high-definition pattern can be obtained.
- a compound having an ethylenically unsaturated group such as (meth) acrylate is used in order to enable rapid curing in the exposure process.
- Patent Document 1 describes a resin composition containing a bismaleimide compound (curable resin) and a photoradical polymerization initiator (curing agent) as a photosensitive resin composition used for a laminated board or a resin sheet.
- curable resin bismaleimide compound
- curing agent photoradical polymerization initiator
- Patent Document 2 describes a resin composition containing a polyvalent carboxy group-containing compound obtained by reacting bismaleimide with monoamine and then reacting with an acid anhydride, and a curable resin such as an epoxy resin. is there. Then, Patent Document 2 describes a polyvalent carboxy group-containing compound capable of obtaining a cured product having alkali developability.
- Patent Document 1 a bismaleimide compound is used as a curable resin, but since the maleimide compound usually has poor light transmittance, if the maleimide compound is contained, the light does not sufficiently reach the photocuring initiator. The photocuring initiator is less likely to generate radicals and its reactivity is very low. Therefore, in Patent Document 1, the maleimide compound is cured by performing additional heating before development, but since heating is involved, a high-definition resist pattern cannot be obtained. Further, since the resin composition described in Patent Document 1 does not have sufficient alkali developability in the first place, an unexposed resin composition remains even after development. Therefore, from this point as well, Patent Document 1 cannot obtain a high-definition resist pattern and cannot be used for manufacturing a high-density printed wiring board.
- the polyvalent carboxy group-containing compound described in Patent Document 2 needs to be obtained by reacting bismaleimide with a monoamine and then reacting with an acid anhydride, so that the process is complicated. Further, since an aromatic amine compound is used as the monoamine, this polyvalent carboxy group-containing compound contains an amide group having an aromatic ring in its structure. Therefore, this multivalent carboxy group-containing compound has poor light transmittance and inhibits the photocuring reaction, so that it is difficult to actually use it in a photosensitive resin composition.
- a resin composition containing a maleimide compound usually has poor compatibility between the maleimide compound and other compounds, and therefore has poor solubility in an organic solvent. It was found that it is difficult to use such a resin composition for varnish. On the other hand, the present inventors have found that the resin sheet obtained even when dried has a strong tack property because the varnish containing a maleimide compound and having excellent solubility has many liquid components.
- the present invention has been made in view of the above problems, and is good when it has good solubility and photocurability and contains a photopolymerization initiator and a compound containing one or more carboxyl groups. It is an object of the present invention to provide a resin composition capable of obtaining a resin sheet having more alkaline developability and suppressed tackiness, a resin sheet using the same, a multilayer printed wiring board, and a semiconductor device.
- the resin composition containing the compound (B) has good solubility and photocurability, and has good solubility when further containing a photopolymerization initiator and a compound containing one or more carboxyl groups. And has excellent alkali developability while having photocurability, and in the resin sheet obtained from the resin composition, tack property is satisfactorily suppressed while having photocurability and alkali developability. This has led to the completion of the present invention.
- a resin composition comprising at least two maleimide compounds (B) selected from the group consisting of the compounds to be compounded.
- R 1 represents a linear or branched alkylene group having 1 to 16 carbon atoms
- R 2 represents a linear or branched alkaneylene group having 2 to 16 carbon atoms. It represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkaneylene group having 2 to 16 carbon atoms.
- R 3 is an independent hydrogen atom and 1 to 16 carbon atoms, respectively. It represents 16 linear or branched alkyl groups or linear or branched alkenyl groups having 2 to 16 carbon atoms.
- N 1 independently represents an integer of 1 to 10).
- R 4 , R 5 , and R 6 may each independently have a hydrogen atom, a hydroxyl group, or a substituent, and have a linear or branched form having 1 to 6 carbon atoms.
- N 2 represents an integer of 1 to 10).
- R 7 independently represents a hydrogen atom or a methyl group.
- N 3 represents an integer of 1 to 10.
- R 8 , R 9 , and R 10 are linear or branched alkyl groups having 1 to 8 carbon atoms, each of which may independently have a hydrogen atom or a substituent. Shows.).
- R 11 independently represents a hydrogen atom, a methyl group, or an ethyl group
- R 12 independently represents a hydrogen atom or a methyl group.
- R 13 independently represents a hydrogen atom, a methyl group, or an ethyl group).
- R 14 independently represents a hydrogen atom or a methyl group.
- N 4 represents an integer of 1 to 10.
- R 15 independently represents a group represented by the following formula (9) or a phenyl group).
- ⁇ * indicates a bond
- R 16 independently represents a hydrogen atom or a methyl group
- the compound (D) containing one or more carboxy groups is a compound represented by the following formula (10), a compound represented by the following formula (11), a compound represented by the following formula (12), and the like.
- R 17 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, or an aminomethyl group.
- K represents an integer of 1 to 5 independently.
- it when it has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other).
- R 18 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- L is an integer of 1 to 9 independently.
- two or more carboxy groups when they are present, they may be acid anhydrides formed by connecting them to each other.
- they when they have a carboxymethyl group. May be an acid anhydride formed by linking a carboxymethyl group and a carboxy group to each other).
- R 19 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- M is an integer of 1 to 9 independently.
- it when it has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other.
- it when it has a carboxymethyl group. May be an acid anhydride formed by linking a carboxymethyl group and a carboxy group to each other).
- R 20 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- O is an integer of 1 to 5 independently.
- carboxy when it has one or more carboxy groups, it may be an acid anhydride formed by connecting the carboxymethyl group and the carboxy group to each other.
- carboxy when it has two or more groups, it may be an acid anhydride formed by connecting them to each other.
- the formula (13) when it has two or more carboxymethyl groups, they are connected to each other. It may be an acid anhydride formed in the above.
- [6] It has a support and a resin layer arranged on one side or both sides of the support, and the resin layer contains the resin composition according to any one of [1] to [5].
- Resin sheet. [7] The resin sheet according to [6], wherein the resin layer has a thickness of 1 to 50 ⁇ m.
- It has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the conductor layer contains the resin composition according to any one of [1] to [5].
- Multi-layer printed wiring board. [9] A semiconductor device comprising the resin composition according to any one of [1] to [5].
- the present invention has good solubility and photocurability, and further has good alkali developability when it contains a photopolymerization initiator and a compound containing one or more carboxyl groups, and then tacks. It is possible to provide a resin composition capable of obtaining a resin sheet whose properties are suppressed, a resin sheet using the same, a multilayer printed wiring board, and a semiconductor device.
- FIG. 1 is a 1 H-NMR chart of an amic acid compound (MA-TMDA).
- FIG. 2 is a 1 H-NMR chart of a maleimide compound (TMDM).
- 6 is a photograph after alkali development performed using a resin sheet obtained by using an active energy ray containing a wavelength of 405 nm (h line) in Example 1 and Comparative Example 6.
- the present embodiment a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be appropriately modified and carried out within the scope of the gist thereof.
- (meth) acryloxy means both “acryloxy” and the corresponding "methacryloxy
- (meth) acrylate means both “acrylate” and the corresponding “methacrylate”.
- (meth) acrylic means both “acrylic” and the corresponding "methacryl”.
- the resin composition of the present embodiment includes a specific bismaleimide compound (A), a compound represented by the formula (2), a compound represented by the formula (3), a compound represented by the formula (4), and a formula. It contains at least two maleimide compounds (B) selected from the group consisting of the compound represented by (5), the compound represented by the formula (6), and the compound represented by the formula (7).
- A specific bismaleimide compound
- B maleimide compounds
- the resin composition contains a bismaleimide compound (A) (also referred to as a component (A)).
- the bismaleimide compound (A) contains a structural unit represented by the formula (1) and maleimide groups at both ends of the molecular chain.
- R 1 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkaneylene group having 2 to 16 carbon atoms.
- R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkaneylene group having 2 to 16 carbon atoms.
- R 3 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
- n 1 independently represents an integer of 1 to 10.
- the present inventors presume that the resin composition has excellent photocuring reactivity by containing the maleimide compound (B) together with the bismaleimide compound (A) for the following reasons.
- the maleimide compound has poor light transmittance, so if the resin composition contains the maleimide compound, the light does not sufficiently reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator radically transfers radicals. Hard to occur. Therefore, in general, the photoradical reaction of the maleimide compound is difficult to proceed, and even if the radical polymerization or dimerization reaction of the maleimide alone proceeds, the reactivity is very low.
- the bismaleimide compound (A) has a structural unit represented by the formula (1), that is, an alicyclic skeleton, it is extremely excellent in light transmission. Therefore, sufficient light reaches the photo-curing initiator, the photoradical reaction of maleimide occurs efficiently, and the bismaleimide compound (A) and the maleimide compound (B) described later are blended as necessary, which will be described later. It can be photo-cured using various active energy rays together with the photo-curing initiator (C) and the compound (D) containing one or more carboxyl radicals described later.
- a chloroform solution containing 1% by mass of the bismaleimide compound (A) is prepared, and an active energy ray containing a wavelength of 365 nm (i-ray) is used to prepare a chloroform solution containing 1% by mass of the bismaleimide compound (A).
- the transmittance of the above is measured, the transmittance is 5% or more, which is very excellent light transmittance.
- the transmittance of a chloroform solution containing 1% by mass of the bismaleimide compound (A) is measured using an active energy ray containing a wavelength of 405 nm (h ray), the transmittance is 5% or more. , Shows very good light transmittance.
- the transmittance at a wavelength of 365 nm (i-line) is preferably 8% or more, and more preferably 10% or more, from the viewpoint of exhibiting more excellent light transmittance.
- the transmittance at a wavelength of 405 nm (h line) is preferably 8% or more, preferably 10% or more, from the viewpoint of producing a printed wiring board having a higher density and high-definition wiring formation (pattern). More preferred.
- the upper limits of the transmittance at the wavelength of 365 nm (i-line) and the transmittance at the wavelength of 405 nm (h-line) are, for example, 99.9% or less.
- photocuring initiators tend to have lower absorbance with respect to light in the long wavelength region.
- an active energy ray (light ray) having a wavelength of 405 nm (h ray) when used, the light having a wavelength of this wavelength is relatively long, so that the light is not absorbed by a normal photocuring initiator, and this light is suitable.
- the polymerization does not proceed unless a photocuring initiator that can absorb the light and generate a radical is used. Therefore, as the photocuring initiator (C) described later, when the absorbance of the chloroform solution containing the photocuring initiator (C) in an amount of 0.01% by mass is measured, the light has a wavelength of 405 nm (h line).
- the bismaleimide compound (A) is excellent in light transmission as described above, for example, even when an active energy ray containing a wavelength of 365 nm or an active energy ray containing 405 nm is used, the light is sufficient to the photoinitiator.
- the radical reaction using the radicals generated from the photo-curing initiator proceeds, and photo-curing is possible even in a composition containing a large amount of the bismaleimide compound (A).
- the present inventors have described that the resin sheet obtained from the resin composition having good solubility has good photocurability and alkali developability, but the tackiness is satisfactorily suppressed. I presume that it depends on the reason.
- the resin composition containing the maleimide compound has poor compatibility with each other, or with the maleimide compound and other compounds such as a photopolymerization initiator and a compound containing one or more carboxy groups. Therefore, the solubility in an organic solvent is poor, and it is difficult to varnish such a resin composition.
- the resin sheet obtained even if the varnish is dried has a strong tack property.
- a resin composition obtained by mixing at least two or more of the bismaleimide compound (A) and the specific maleimide compound (B) described later is excellent while having excellent photocurability. Since it has compatibility with other substances, it has good solubility in organic solvents. On top of that, when used in a varnish, since the amount of liquid components in the varnish is small, the resin sheet obtained by drying the varnish has good tackiness.
- maleimide compounds usually have extremely low water solubility and do not have reactivity with alkaline components in an alkaline developer, it is difficult to obtain alkaline developability.
- the bismaleimide compound (A) and the maleimide compound (B) together with the photocuring initiator (C) described later and the compound (D) containing one or more carboxyl groups described below it is possible to obtain a resin composition having excellent photocurability and solubility in an organic solvent, and having excellent alkali developability. The reason for this is not clear, but the present inventors presume as follows.
- the bismaleimide compound (A) has a relatively long chain and a flexible structure, and does not have a structure that causes an interaction with an alkaline component in an alkaline developer. Further, neither the maleimide compound (B) nor the initiator (C) has a structure that causes an interaction with an alkaline component in an alkaline developer. Therefore, these compounds (A), (B) and the initiator (C) are dissolved in the alkaline developer while maintaining the structure of the compound (D) in the alkaline developer. It can be dissolved in an alkaline developer.
- the alkaline developer flows into the unexposed portion (resin composition), it is contained in the alkaline developer without being hindered by these compounds (A), (B) and the initiator (C).
- the alkaline component and the carboxy group in the compound (D) can quickly and preferably form a salt, and the water solubility is improved. Therefore, it is presumed that the resin composition has excellent alkali developability.
- the varnish obtained from this resin composition also has a small amount of liquid components, so that the resin sheet obtained by drying the varnish has good tackiness.
- the cured product obtained from the resin composition is excellent in heat resistance, insulation reliability, and thermal stability. Therefore, according to the present embodiment, the protective film and the insulating layer in the multilayer printed wiring board and the semiconductor device can be suitably formed.
- the bismaleimide compound (A) is not particularly limited as long as it exerts the effect of the present invention, but the mass average molecular weight is preferably 100 to 5000 from the viewpoint that a suitable viscosity can be obtained and an increase in the viscosity of the varnish can be suppressed. , 300-4500, more preferably.
- the "mass average molecular weight” means the polystyrene standard equivalent mass average molecular weight by the gel permeation chromatography (GPC) method.
- R 1 has a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkaneylene group having 2 to 16 carbon atoms. Shown. R 1 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group, from the viewpoint that a suitable viscosity can be obtained and an increase in the viscosity of the varnish can be controlled.
- the number of carbon atoms of the alkylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled.
- Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, a 2,2-dimethylpropylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group and a decylene.
- the number of carbon atoms of the alkenylene group is preferably 2 to 14 and more preferably 4 to 12 from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled.
- the linear or branched alkenylene group include a vinylene group, a 1-methylvinylene group, an allylene group, a propenylene group, an isopropenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, and 2 -Pentenylene group, isopentylene group, cyclopentenylene group, cyclohexenylene group, dicyclopentadienylene group and the like can be mentioned.
- R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkaneylene group having 2 to 16 carbon atoms.
- R 2 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group, from the viewpoint that a suitable viscosity can be obtained and an increase in the viscosity of the varnish can be controlled.
- the number of carbon atoms of the alkylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled.
- the linear or branched alkylene group the above-mentioned R 1 can be referred to.
- the number of carbon atoms of the alkenylene group is preferably 2 to 14 and more preferably 4 to 12 from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled.
- the linear or branched alkenylene group the above-mentioned R 1 can be referred to.
- R 1 and R 2 may be the same or different, but are preferably the same from the viewpoint that the bismaleimide compound (A) can be more easily synthesized.
- R 3 independently comprises a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
- R 3 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms independently from the viewpoint that a suitable viscosity can be obtained and the increase in the viscosity of the varnish can be controlled.
- the group (R 3 ) of 1 to 5 is a linear or branched alkyl group having 1 to 16 carbon atoms, and the remaining group (R 3 ) is a hydrogen atom.
- 1 ⁇ 3 group (R 3) is a straight-chain or branched alkyl group having 1 to 16 carbon atoms, more preferably remaining groups (R 3) is a hydrogen atom.
- the number of carbon atoms of the alkyl group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be more controlled.
- Examples of the linear or branched alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, 1-ethylpropyl group, n-butyl group, 2-butyl group, isobutyl group and tert-butyl.
- n-pentyl group 2-pentyl group, tert-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, Examples thereof include n-heptyl group, n-octyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2-methylpentane-3-yl group, and n-nonyl group.
- the number of carbon atoms of the alkenyl group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be more controlled.
- Examples of the linear or branched alkenyl group include a vinyl group, an allyl group, a 4-pentenyl group, an isopropenyl group, an isopentenyl group, a 2-heptenyl group, a 2-octenyl group, and a 2-nonenyl group. Be done.
- n 1 independently represents an integer of 1 to 10.
- the bismaleimide compound (A) has maleimide groups at both ends of the molecular chain. Both ends mean both ends in the molecular chain of the bismaleimide compound (A), and for example, when the structural unit represented by the formula (1) is at the end of the molecular chain of the bismaleimide compound (A). Means that the maleimide group is present at the end of the molecular chain of R 1 , at the end of the molecular chain at the N atom of the maleimide ring, or at both ends.
- the bismaleimide compound (A) may have a maleimide group in addition to both ends of the molecular chain.
- the maleimide group is represented by the formula (14), and the N atom is bonded to the molecular chain of the bismaleimide compound (A). Further, the maleimide groups bonded to the bismaleimide compound (A) may be all the same or different, but it is preferable that the maleimide groups at both ends of the molecular chain are the same.
- R 21 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Both of R 21 are preferably hydrogen atoms from the viewpoint of being preferably photocured. The number of carbon atoms of the alkyl group is preferably 1 to 3 and more preferably 1 to 2 from the viewpoint of being preferably photocured. As the linear or branched alkyl group, the above-mentioned R 3 can be referred to.
- Examples of such a bismaleimide compound (A) include a maleimide compound represented by the formula (15). These can be used alone or in admixture of two or more.
- a represents an integer from 1 to 10.
- a is preferably an integer of 1 to 6 from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be more controlled.
- the bismaleimide compound (A) a commercially available product can also be used.
- examples of commercially available products include MIZ-001 manufactured by Nippon Kayaku Co., Ltd. (including a maleimide compound having a trade name of formula (15)).
- the content of the bismaleimide compound (A) has better compatibility with the maleimide compound (B) described later, and it becomes possible to obtain a cured product containing the bismaleimide compound as a main component.
- the bismaleimide compound (A) and It is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 35 to 75 parts by mass with respect to 100 parts by mass of the total of the maleimide compound (B) described later. ..
- the bismaleimide compound (A) can be used alone or in admixture of two or more.
- the bismaleimide compound (A) can be produced by a known method.
- 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, a monomer containing a diamine containing dimerdiamine and the like, and maleic anhydride are usually about 80 to 250 ° C, preferably about 100 to 200 ° C.
- a heavy adduct reaction is carried out to obtain a heavy adduct, and then usually about 60 to 120 ° C., preferably about 80 to 100 ° C.
- the bismaleimide compound (A) can be obtained by subjecting the heavy adduct to an imidization reaction, that is, a dehydration ring closure reaction, usually for about 0.1 to 2 hours, preferably about 0.1 to 0.5 hours. it can.
- Dimer diamine is obtained, for example, by a reductive amination reaction of dimer acid, and the amineization reaction is described in a known method such as a reduction method using ammonia and a catalyst (for example, JP-A-9-12712). It can be done by the method of).
- Dimer acid is a dibasic acid obtained by dimerizing unsaturated fatty acids by an intermolecular polymerization reaction or the like. Although it depends on the synthesis conditions and purification conditions, it usually contains a small amount of monomeric acid, trimer acid and the like in addition to dimer acid.
- Dimeric acid is obtained, for example, by polymerizing unsaturated fatty acids using Lewis acid and Bronsted acid as catalysts. Dimeric acid can be produced by a known method (for example, the method described in JP-A-9-12712).
- unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, baxenoic acid, gadrainic acid, eicosaenoic acid, erucic acid, nervonic acid, linoleic acid, pinolenic acid and eleostearic acid.
- the unsaturated fatty acid usually has 4 to 24 carbon atoms, preferably 14 to 20 carbon atoms.
- the diamine-containing monomer is previously dissolved in an organic solvent or dispersed in a slurry in an inert atmosphere such as argon or nitrogen to form a diamine-containing monomer solution. It is preferable to do so. Then, 1,2,4,5-cyclohexanetetracarboxylic dianhydride can be added to the monomer solution containing the diamine after being dissolved in an organic solvent or dispersed in a slurry, or in a solid state. preferable.
- An arbitrary bismaleimide compound (A) can be obtained by preparing the number of moles of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and the total number of moles of the diamine-containing monomer and the maleimide compound. be able to.
- Solvents include, for example, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; Esters such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate; methanol, ethanol , And aliphatic alcohols having 1 to 10 carbon atoms such as propanol; aromatic group-containing phenols such as phenol and cresol; aromatic group-containing alcohols such as
- glycols with methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, cresol, etc., or glycol ethers such as esters of these monoethers; dioxane, and Examples include ethers such as tetrahydrofuran; cyclic carbonates such as ethylene carbonate and propylene carbonate; aromatic hydrocarbons such as aliphatic and toluene, and xylene; aprotonic polar solvents such as dimethyl sulfoxide. These solvents may be used alone or in combination of two or more, if necessary.
- a catalyst for example, a tertiary amine and a dehydration catalyst can be used.
- a tertiary amine a heterocyclic tertiary amine is preferable, and examples thereof include pyridine, picoline, quinoline, and isoquinoline.
- the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride and the like.
- the amount of the catalyst added is, for example, about 0.5 to 5.0 times the molar equivalent of the imidizing agent with respect to the amide group, and 0.5 to 10.0 times the molar equivalent of the dehydration catalyst with respect to the amide group.
- the equivalent amount is preferable.
- this solution may be used as a bismaleimide compound (A) solution, or a poor solvent may be added to the reaction solvent to make the bismaleimide compound (A) a solid substance.
- the poor solvent include water, methyl alcohol, ethyl alcohol, 2-propyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-pentyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, and phenol. Examples thereof include t-butyl alcohol.
- the resin composition of the present embodiment contains a maleimide compound (B) (also referred to as a component (B)) other than the bismaleimide compound (A) according to the present embodiment.
- the maleimide compound (B) is a compound represented by the formula (2), a compound represented by the formula (3), a compound represented by the formula (4), a compound represented by the formula (5), and a compound represented by the formula (6).
- the maleimide compound (B) is a compound represented by the formula (2), a compound represented by the formula (3), a compound represented by the formula (4), a compound represented by the formula (5), and a compound represented by the formula (6).
- the maleimide compound (B) two or more of the compounds represented by the formulas (2) to (7) can be appropriately mixed and used.
- the bismaleimide compound (A) and the maleimide compound (B) have better solubility, and while being superior in photocurability, the amount of liquid components in the varnish can be reduced, and the tackiness is improved.
- the maleimide compound (B) contains 2 to 4 kinds of compounds represented by the formulas (2) to (7). More preferably, it contains a compound of the species.
- the reactivity of photoradicals of maleimide compounds is usually very low.
- the bismaleimide compound (A) is very excellent in light transmission as described above. Therefore, the bismaleimide compound (A) is used together with the maleimide compound (B), the photocuring initiator (C) described later, and the compound (D) containing one or more carboxyl radicals described later, which are blended as necessary. As a result, sufficient light reaches the photo-curing initiator, the photoradical reaction of maleimide occurs efficiently, and photo-curing can be performed using various active energy rays.
- the bismaleimide compound (A) Since the bismaleimide compound (A) has excellent light transmittance, for example, even if an active energy ray containing a wavelength of 365 nm or an active energy ray containing 405 nm is used, the light sufficiently reaches the photoinitiator and is photocured. The radical reaction using the radicals generated from the initiator proceeds, and photocuring is possible even in the composition containing the maleimide compound (B). Further, the maleimide compound (B) has good compatibility with the bismaleimide compound (A) and has excellent solubility in an organic solvent.
- the maleimide compound (B) when a varnish is prepared by using the maleimide compound (B) together with the bismaleimide compound (A), the maleimide compound (B) can suitably suppress the ratio of the liquid component in the system, so that the varnish is dried.
- the resin sheet thus obtained can be satisfactorily suppressed in tackiness.
- the protective film and the insulating layer can be suitably formed according to the resin composition of the present embodiment.
- R 4 , R 5 , and R 6 may each independently have a hydrogen atom, a hydroxyl group, or a substituent, and are linear or branched with 1 to 6 carbon atoms. Indicates an alkyl group. n 2 represents an integer from 1 to 10. As the linear or branched alkyl group having 1 to 6 carbon atoms, R 3 in the above formula (1) can be referred to. As the alkyl group, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are used from the viewpoint of achieving good solubility in a solvent, low melting point, low water absorption, and good compatibility with other resins.
- R 4 and R 6 are linear or branched alkyl groups having 1 to 6 carbon atoms. Yes, and R 5 is preferably a hydrogen atom.
- the preferred alkyl group is as described above.
- n 2 is preferably an integer of 1 to 10 and preferably an integer of 1 to 6 from the viewpoint of excellent solubility in a solvent, a more suitable viscosity, and more controllable increase in the viscosity of the varnish. More preferred.
- BCPH13 (trade name) manufactured by Gun Ei Chemical Industry Co., Ltd., which is represented by the formula (16)
- BCPH01 trade name manufactured by Gun Ei Chemical Industry Co., Ltd.
- BMCX426 trade name manufactured by Gun Ei Chemical Industry Co., Ltd. represented by the formula (17)
- n 21 is an integer from 1 to 5.
- n 22 is an integer from 1 to 10.
- R 7 independently represents a hydrogen atom or a methyl group.
- n 3 represents an integer from 1 to 10.
- MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. represented by the formula (18).
- n 31 is an integer from 1 to 10.
- R 8 , R 9 , and R 10 each independently have a linear or branched alkyl group having 1 to 8 carbon atoms, which may have a hydrogen atom or a substituent. Shown.
- the linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent is not particularly limited, and is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group or an n-butyl group.
- the hydrogen atom in these alkyl groups may be substituted with a fluorine atom, a halogen atom such as a chlorine atom, a cyano group or the like.
- methyl group, ethyl group, isopropyl group, and tert-butyl group are excellent in photocurability, heat resistance, and thermal stability, and have better solubility in a solvent.
- the compound represented by the formula (4) is a compound represented by the formula (19) because it is excellent in photocurability, heat resistance, and thermal stability, and has better solubility in a solvent. In embodiments, it is even more preferred to be TMDM).
- R 11 independently represents a hydrogen atom, a methyl group, or an ethyl group
- R 12 independently represents a hydrogen atom or a methyl group.
- R 11 is preferably a methyl group or an ethyl group from the viewpoint of exhibiting good solubility in a solvent, low boiling point, low water absorption, and good compatibility with other resins.
- R 12 is preferably a hydrogen atom from the viewpoint of exhibiting good solubility in a solvent, low boiling point, low water absorption, and good compatibility with other resins.
- maleimide compound represented by the formula (5) a commercially available product may be used, and examples thereof include BMI-70 (trade name) manufactured by KAI Kasei Co., Ltd. represented by the formula (20).
- R 13 independently represents a hydrogen atom, a methyl group, or an ethyl group.
- R 13 is preferably a methyl group or an ethyl group from the viewpoint of exhibiting good solubility in a solvent, low boiling point, low water absorption, and good compatibility with other resins.
- the maleimide compound represented by the formula (6) a commercially available product may be used, and examples thereof include BMI-80 (trade name) manufactured by KAI Kasei Co., Ltd. represented by the formula (21).
- R 14 independently represents a hydrogen atom or a methyl group.
- n 4 represents an integer from 1 to 10.
- R 14 is preferably a hydrogen atom from the viewpoint of exhibiting good solubility in a solvent, low boiling point, low water absorption, and good compatibility with other resins.
- n 4 is more preferably an integer of 1 to 5 because it has excellent solubility in a solvent, a more suitable viscosity can be obtained, and an increase in the viscosity of the varnish can be more controlled.
- maleimide compound represented by the formula (7) a commercially available product may be used, and examples thereof include BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. represented by the formula (22).
- n 41 is an integer from 1 to 5.
- the content of the maleimide compound (B) has better compatibility with the bismaleimide compound (A), better heat resistance and thermal stability can be obtained, and further, better tackiness.
- the amount is preferably 10 to 90 parts by mass, preferably 20 to 80 parts by mass, based on 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (B). It is more preferably parts, and even more preferably 25 to 65 parts by mass.
- the resin composition of the present embodiment preferably further contains a photocuring initiator (C) (also referred to as component (C)).
- the photocurable initiator (C) is not particularly limited, and those known in the field generally used in the photocurable resin composition can be used.
- the photo-curing initiator (C) is photo-cured using various active energy rays together with a bismaleimide compound (A), a maleimide compound (B), a compound (D) containing one or more carboxyl groups described later, and the like. Used for
- Examples of the photocuring initiator (C) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, and parachlorobenzoyl.
- Benzoyls such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, and 4,4'-bismethylaminobenzophenone
- 1,2-octanedione 1- [4- (phenylthio)-, 2-( O-benzoyl oxime)]
- oxime esters such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc.
- Radical photocuring initiator and Diazonium salts of Lewis acids such as p-methoxyphenyldiazonium fluorophosphonate and N, N-diethylaminophenyldiazonium hexafluorophosphonate; iodonium salts of Lewis acids such as diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate; triphenyl Sulfonium salts of Lewis acids such as sulfonium hexafluorophosphonate and triphenylsulfonium hexafluoroantimonate; phosphonium salts of Lewis acids such as triphenylphosphonium hexafluoroantimonate; other halides; triazine initiators; borate initiators ; Other cationic photopolymerization initiators such as photoacid generators can be mentioned.
- a commercially available product can also be used, for example, IGM Resins B.I. V. Omnirad® 369 (trade name), IGM Resins B. et al. V. Omnirad® 819 (trade name), IGM Resins B. et al. V. Omnirad® 819DW (trade name), IGM Resins B. et al. V. Omnirad® 907 (trade name), IGM Resins B. et al. V. Omnirad® TPO (trade name), IGM Resins B.I. V. Omnirad® TPO-G (trade name), IGM Resins B.I. V. Omnirad (registered trademark) 784 (trademark), BASF Japan Co., Ltd.
- Irgacure (registered trademark) OXE02 (trademark), BASF Japan Examples thereof include Irgacure (registered trademark) OXE03 (trademark) manufactured by BASF Japan Co., Ltd. and Irgacure (registered trademark) OXE04 (trademark) manufactured by BASF Japan Co., Ltd.
- These photo-curing initiators (C) can be used alone or in admixture of two or more.
- the photoinitiator (C) As the photoinitiator (C), a chloroform solution contained in an amount of 0.01% by mass is prepared, and an active energy ray containing a wavelength of 365 nm (i-line) is used to add 0.01% by mass of the photoinitiator (C).
- the absorbance of the chloroform solution contained in% the absorbance is preferably 0.1 or more, and the photoinitiator (C) exhibits extremely excellent absorbance. Further, when the absorbance of the chloroform solution containing the photoinitiator (C) in an amount of 0.01% by mass is measured using an active energy ray containing a wavelength of 405 nm (h line), the absorbance is 0.1.
- the above is preferable, and even in this case, very excellent absorbance is exhibited.
- a photocuring initiator (C) for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured by using a direct drawing exposure method, a wavelength of 405 nm (h line) is used. Even when an active energy ray containing is used, the photoradical reaction of maleimide occurs efficiently.
- the absorbance at a wavelength of 365 nm (i-line) is more preferably 0.15 or more because a resin composition having better photocurability can be obtained.
- the absorbance at a wavelength of 405 nm (h line) is more preferably 0.15 or more because a resin composition having better photocurability can be obtained.
- the upper limits of the absorbance at the wavelength of 365 (i-line) and the absorbance at the wavelength of 405 nm (h-line) are, for example, 99.9 or less.
- a compound represented by the formula (8) is preferable.
- R 15 independently represents a substituent or phenyl group represented by formula (9).
- R 16 independently represents a hydrogen atom or a methyl group.
- ⁇ * indicates a bond with a phosphorus atom (P) directly connected to R 15 in formula (8).
- a chloroform solution containing 0.01% by mass of this compound was prepared, and the absorbance of this chloroform solution was measured using an active energy ray containing a wavelength of 365 nm (i-ray).
- the absorbance is 0.1 or more, and it exhibits extremely excellent absorbency for light having a wavelength of 365 nm (i-line). Therefore, this compound preferably generates radicals for light having a wavelength of 365 nm (i-line).
- the absorbance is preferably 0.15 or more.
- the upper limit is, for example, 10.0 or less, 5.0 or less, or 2.0 or less.
- a chloroform solution containing 0.01% by mass of this compound was prepared, and the absorbance of this chloroform solution was measured using an active energy ray containing a wavelength of 405 nm (h line).
- the absorbance is 0.1 or more, and it exhibits extremely excellent absorbency for light having a wavelength of 405 nm (h line). Therefore, this compound preferably generates radicals for light having a wavelength of 405 nm (h line).
- the absorbance is more preferably 0.15 or more.
- the upper limit is, for example, 10.0 or less, 5.0 or less, or 2.0 or less.
- R 15 independently represents a substituent or phenyl group represented by formula (9). It is preferable that one or more of R 15 are substituents represented by the formula (9).
- R 16 independently represents a hydrogen atom or a methyl group. Of R 16 , it is preferable that one or more are methyl groups, and it is more preferable that all of them are methyl groups.
- Examples of the compound represented by the formula (8) include acyls such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
- Examples include phosphine oxides.
- bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferable because it has excellent light transmittance. These compounds may be used alone or in admixture of two or more.
- Acylphosphine oxides show extremely excellent absorption to active energy rays including a wavelength of 405 nm (h line), for example, at a wavelength of 405 nm (h line), a bismaleimide compound (A) and a maleimide compound. (B) can be suitably radically polymerized. Further, the acylphosphine oxides are well compatible with the bismaleimide compound (A) and the maleimide compound (B), and are well dissolved in an organic solvent. Furthermore, since the acylphosphine oxides can exist as a solid after removing the solvent in the varnish, the liquid component in the varnish can be further reduced.
- acylphosphine oxides it is possible to preferably obtain a resin composition having excellent solubility and photocurability, and a resin sheet having excellent photocurability and capable of satisfactorily suppressing tackiness. Further, it becomes possible to suitably manufacture a multilayer printed wiring board and a semiconductor device using them.
- the content of the photocuring initiator (C) has better compatibility with the bismaleimide compound (A) and the maleimide compound (B), and the photocuring of these compounds is sufficiently advanced to develop alkali.
- the resin composition of the present embodiment preferably further contains a compound (D) containing one or more carboxyl groups (also referred to as a component (D) or a compound (D)).
- the compound (D) is not particularly limited as long as it contains one or more carboxy groups in the compound.
- the carboxy group may be a salt such as a sodium salt and a potassium salt, and when two or more carboxy groups are contained in the molecule, it may be an acid anhydride formed by connecting them to each other.
- Compound (D) may be used alone or in admixture of two or more.
- Compound (D) is photocured using various active energy rays together with the bismaleimide compound (A) and maleimide compound (B) according to the present embodiment and, if necessary, a photocuring initiator (C). , A cured product can be obtained. Further, according to the present embodiment, a resin composition containing the compound (D) can be obtained in the unexposed portion.
- compound (D) prepare an N-methylpyrrolidone solution containing 1% by mass, and use active energy rays containing a wavelength of 365 nm (i-line) to contain N-methyl containing 1% by mass of compound (D). When the transmittance of the pyrrolidone solution is measured, the transmittance is preferably 5% or more.
- compound (D) exhibits extremely excellent light transmission. Further, when the transmittance of the N-methylpyrrolidone solution containing 1% by mass of the compound (D) is measured using an active energy ray containing a wavelength of 405 nm (h ray), the transmittance is 5% or more. Is preferable, and even in this case, very excellent light transmittance is exhibited.
- a compound (D) for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is produced by using a direct drawing exposure method, an activity containing a wavelength of 405 nm (h line) is included. Even when energy rays are used, the photoradical reaction of maleimide occurs efficiently.
- the transmittance at a wavelength of 365 nm (i-line) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more in this order because a resin composition having better photocurability can be obtained. Is a preferable range.
- the transmittance at a wavelength of 405 nm (h line) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more in this order because a resin composition having better photocurability can be obtained. Is a preferable range.
- the upper limits of the transmittance at the wavelength of 365 nm (i-line) and the transmittance at the wavelength of 405 nm (h-line) are, for example, 99.9% or less.
- the molecule of compound (D) contains a carboxy group as an integer of 2 to 4 from the viewpoint of obtaining more excellent alkali developability.
- the molecular weight of compound (D) is preferably 50 to 1000, more preferably 100 to 800, from the viewpoint of further improving developability.
- Examples of the compound (D) include formic acid, an aliphatic compound containing one or more carboxy groups, an aromatic compound containing one or more carboxy groups, and a hetero compound containing one or more carboxy groups. These compounds (D) can be used alone or in admixture of two or more.
- aliphatic compound containing one or more carboxy groups examples include a chain aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, a chain aliphatic polyvalent carboxylic acid, and an alicyclic polyvalent carboxylic acid. .. These compounds have a hydrogen atom and a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxyl group, an amino group, and a carboxyalkyl group in the molecule. May be good.
- these compounds when they have two or more carboxy groups in the molecule, they may be acid anhydrides formed by connecting them to each other.
- they when these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by connecting the carboxyalkyl group and the carboxy group to each other.
- they When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them to each other.
- alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and n.
- -Heptyl group and n-octyl group can be mentioned.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, an n-hexanoxy group, a 2-methylpropoxy group and the like.
- Examples of the aryloxy group include a phenoxy group and a p-tolyloxy group.
- Examples of the aryl group include a phenyl group, a toluyl group, a benzyl group, a methylbenzyl group, a xsilyl group, a mesityl group, a naphthyl group, and an anthryl group.
- aminoalkyl group examples include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminodimethyl group, an aminodiethyl group, an aminodipropyl group, an aminobutyl group, an aminohexyl group, an aminononyl group and the like.
- carboxyalkyl group examples include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, a carboxyhexyl group, a carboxynonyl group and the like.
- chain aliphatic monocarboxylic acid examples include acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, caproic acid, lactic acid, succinic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid and tetradecane.
- Saturated fatty acids such as acids, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid
- unsaturated fatty acids such as oleic acid, ellaic acid, erucic acid, nervonic acid, linolenic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid
- unsaturated fatty acids such as oleic acid, ellaic acid, erucic acid, nervonic acid, linolenic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid
- Examples of the alicyclic monocarboxylic acid include cyclopropanecarboxylic acid, cyclopropenecarboxylic acid, cyclobutanecarboxylic acid, cyclobutenecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, and cycloheptanecarboxylic acid.
- Monocyclic carboxylic acids such as acids, cycloheptene carboxylic acids, cyclooctane carboxylic acids, and cyclooctene carboxylic acids, norbornan carboxylic acids, tricyclodecane carboxylic acids, tetracyclododecane carboxylic acids, adamantan carboxylic acids, methyl adamantan carboxylic acids , Ethyladamantancarboxylic acid, polycyclic or abridged alicyclic carboxylic acid such as butyladamantancarboxylic acid, and the like.
- Examples of the chain aliphatic polyunsaturated carboxylic acid include a carboxylic acid in which one or more carboxy groups are further added to the chain aliphatic monocarboxylic acid.
- a carboxylic acid in which one or more carboxy groups are further added to the chain aliphatic monocarboxylic acid for example, propion diic acid, octane diic acid, nonane diic acid, decane diic acid, dodecane diic acid, tetradecane diic acid, hexadecane diic acid, heptadecane diic acid, octadecane diic acid and the like can be mentioned.
- Examples of the alicyclic polyvalent carboxylic acid include a carboxylic acid in which one or more carboxy groups are further added to the alicyclic monocarboxylic acid.
- a carboxylic acid in which one or more carboxy groups are further added to the alicyclic monocarboxylic acid.
- Aromatic compound containing one or more carboxy groups examples include benzoic acid, phenylene acetic acid, salicylic acid, phthalic acid, trimeric acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphthalenecarboxylic acid, and naphthalene.
- Aromatic compounds have, for example, a hydrogen atom and an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxyl group, an amino group, a carboxyalkyl group and the like on the aromatic ring of these parent skeletons. It may have a substituent.
- these compounds when they have two or more carboxy groups in the molecule, they may be acid anhydrides formed by connecting them to each other.
- they when these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by connecting the carboxyalkyl group and the carboxy group to each other.
- these compounds When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them to each other. The above can be referred to for these substituents.
- heterocompound containing one or more carboxy groups examples include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrridine, piperidine, piperazine, morpholine, indol, purine, quinoline, isoquinoline, and quinuclysine. , Chromen, thiantorene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, and carbazole and the like, and examples thereof include compounds containing one or more carboxy groups in the heterocycle.
- the hetero compound has, for example, a hydrogen atom and a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxyl group, an amino group, and a carboxyalkyl group on these parent skeletons. You may be doing it. Further, when these compounds have two or more carboxy groups in the molecule, they may be acid anhydrides formed by connecting them to each other. When these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by connecting the carboxyalkyl group and the carboxy group to each other. When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them to each other. The above can be referred to for these substituents.
- a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxyl group
- the compound (D) is represented by a compound represented by the formula (10), a compound represented by the formula (11), and a compound represented by the formula (12) from the viewpoint that excellent alkali developability can be imparted to the resin composition.
- the compound and the compound represented by the formula (13) are preferable, and the compound represented by the formula (12) is more preferable from the viewpoint of imparting more excellent alkali developability to the resin composition.
- the compound represented by the formula (10) is as follows.
- R 17 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, or an aminomethyl group. Further, when the compound represented by the formula (10) has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other. In formula (10), the upper limit of the number of carboxy groups is 6. R 17 is preferably a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group independently from the viewpoint of alkali developability, and contains a carboxy group from the viewpoint of obtaining more excellent alkali developability. Is more preferable. Benzoic acid tends to be inferior in alkali developability as compared with compound (D) containing one or more other carboxy groups. Further, k independently represents an integer of 1 to 5.
- the compound represented by the formula (10) is preferably the compound represented by the formula (23) from the viewpoint of obtaining more excellent alkali developability.
- R 17 independently represents a hydrogen atom, a hydroxyl group, an amino group, or an aminomethyl group.
- R 17 is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom, from the viewpoint of exhibiting more excellent alkali developability.
- k independently represents an integer of 0 to 4.
- the carboxy cardinal number p represents an integer of 5-k.
- the carboxy group number p is preferably an integer of 1 to 3 from the viewpoint of exhibiting more excellent alkali developability.
- the number k of R 17 is an integer of 5-p and an integer of 2 to 4.
- the compound represented by the formula (23) may be an acid anhydride containing two or more carboxy groups and formed by connecting them to each other.
- Examples of the compound represented by the formula (10) include 4-aminobenzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, 4-aminomethylbenzoic acid, and anhydrides thereof.
- Examples of these anhydrides include phthalic acid anhydride, trimellitic acid anhydride, and pyromellitic acid anhydride.
- the compound represented by the formula (10) is preferably phthalic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof from the viewpoint of obtaining more excellent alkali developability.
- the compound represented by the formula (11) is as follows.
- R 18 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group. Further, when the compound represented by the formula (11) has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other. In formula (11), the upper limit of the number of carboxy groups is 10. When the compound represented by the formula (11) has a carboxymethyl group, it may be an acid anhydride formed by connecting the carboxymethyl group and the carboxy group to each other.
- R 18 is preferably a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group independently from the viewpoint of alkali developability, and contains a carboxy group from the viewpoint of obtaining more excellent alkali developability. Is more preferable. Further, l independently represents an integer of 1 to 9. The piperidine carboxylic acid tends to be inferior in alkali developability as compared with the compound (B) containing one or more other carboxy groups.
- R 18 contains a carboxy group
- the number of carboxy groups l is preferably 1 to 3 from the viewpoint of alkali developability.
- the R 5 other than the carboxy group is preferably a hydrogen atom or a hydroxyl group independently, and more preferably a hydrogen atom.
- the compound represented by the formula (11) contains a carboxy group of 1 to 3, the number of R 5 other than the carboxy group is 7 to 9.
- Examples of the compound represented by the formula (11) include piperidinecarboxylic acid, 1,2-piperidindicarboxylic acid, and piperidinedicarboxylic acid anhydride.
- the compound represented by the formula (12) is as follows.
- R 19 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group. Further, when the compound represented by the formula (12) has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other. In formula (12), the upper limit of the number of carboxy groups is 10. When the compound represented by the formula (12) has a carboxymethyl group, it may be an acid anhydride formed by connecting the carboxymethyl group and the carboxy group to each other.
- R 19 is preferably a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group independently from the viewpoint of alkali developability, and contains a carboxy group from the viewpoint of obtaining more excellent alkali developability. Is more preferable. Further, m independently represents an integer of 1 to 9.
- the compound represented by the formula (12) is preferably a compound represented by the formula (24) from the viewpoint of obtaining more excellent alkali developability.
- R 19 independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group, or an aminomethyl group.
- R 19 is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom, from the viewpoint of exhibiting more excellent alkali developability.
- m independently represents an integer of 0 to 8.
- the carboxy cardinal number q represents an integer of 9-m.
- the carboxy group number q is preferably an integer of 1 to 3 from the viewpoint of exhibiting more excellent alkali developability.
- the number m of R 6 is an integer of 9-q and an integer of 6 to 8.
- the compound represented by the formula (24) may be an acid anhydride containing two or more carboxy groups and formed by connecting them to each other.
- the carboxymethyl group and the carboxy group may be an acid anhydride formed by connecting them to each other.
- Examples of the compound represented by the formula (12) include 3-cyclohexene-1-carboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. Things can be mentioned.
- cis-4-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic acid are obtained from the viewpoint of obtaining more excellent alkali developability. It is preferably an anhydride.
- the compound represented by the formula (13) is as follows.
- R 20 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- the compound represented by the formula (13) may be an acid anhydride formed by connecting the carboxymethyl group and the carboxy group to each other.
- it may be an acid anhydride formed by connecting them to each other.
- the upper limit of the number of carboxy groups is 5.
- the upper limit of the number of carboxymethyl groups is 6.
- R 20 preferably contains a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group independently from the viewpoint of alkali developability, and contains a carboxy group from the viewpoint of obtaining more excellent alkali developability. Is more preferable. Further, o independently represents an integer of 1 to 5.
- the compound represented by the formula (13) is preferably a compound represented by the formula (25) from the viewpoint of obtaining more excellent alkali developability.
- R 20 independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group, or an aminomethyl group.
- R 20 is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom, from the viewpoint of exhibiting more excellent alkali developability.
- o independently represents an integer of 0 to 4.
- the carboxy cardinal number r represents an integer of 5-o.
- the number of carboxy groups r is preferably an integer of 1 to 3 from the viewpoint of exhibiting more excellent alkali developability.
- the number o of R 7 is an integer of 5-r and an integer of 2 to 4.
- the carboxymethyl group and the carboxy group may be acid anhydrides formed by connecting them to each other.
- the compound represented by the formula (25) has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other.
- the upper limit of the number of carboxy groups is 5.
- the compound represented by the formula (25) has two or more carboxymethyl groups, it may be an acid anhydride formed by connecting them to each other.
- the upper limit of the number of carboxymethyl groups is 6.
- Examples of the compound represented by the formula (13) include phenylene acetic acid, 1,2-phenylene diacetic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, and anhydrides thereof.
- Examples of these anhydrides include 1,2-phenylene diacetate anhydride.
- the compound represented by the formula (13) is preferably 1,2-phenylene diacetic acid from the viewpoint of obtaining more excellent alkali developability.
- the compound (D) containing one or more of these carboxy groups can be used alone or in admixture of two or more.
- the content of the compound (D) containing one or more carboxyl groups has better compatibility with the bismaleimide compound (A) and the maleimide compound (B), and the liquid component in the varnish is less. It is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (B) from the viewpoint that it can be obtained and more excellent alkali developability can be imparted. It is more preferably 0.5 to 20 parts by mass, further preferably 1 to 15 parts by mass.
- a maleimide compound (E) other than bismaleimide compound (A) and maleimide compound (B) may be used as long as the effects of the present invention are exhibited. it can.
- the bismaleimide compound (A) is extremely excellent in light transmission. Therefore, even if the maleimide compound (E) is used together with the maleimide compound (B), sufficient light reaches the photocuring initiator, and the maleimide compound. Photoradical reactions occur efficiently and can be photocured using various active energy rays.
- the light sufficiently reaches the photocuring initiator, and the radical reaction using the radical generated from the photocuring initiator proceeds.
- photocuring is also possible in the composition containing the maleimide compound (E).
- the maleimide compound (E) a maleimide compound having better compatibility with the bismaleimide compound (A) and the maleimide compound (B) and having a reduced liquid component in the varnish when used in a varnish. It is preferable to use it.
- the maleimide compound (E) is other than the bismaleimide compound (A) and the maleimide compound (B), and is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule.
- 4,4-Maleimide butyric acid bis (4-maleimidephenyl) methane, 2,2-bis (4- (4-maleimidephenoxy) -phenyl) propane, 4,4-diphenylmethanebismaleimide, bis (3,5-dimethyl- 4-Maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, phenylmethanemaleimide, o-phenylenebismaleimide, m -Phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis (4- (4-maleimide phenoxy) -phenyl) propane , 3,3-Dimethyl-5,5-diethy
- the content of the maleimide compound (E) is usually 1 to 30 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- a filler (F) (also referred to as a component (F)) can be used in order to improve various properties such as coating film property and heat resistance.
- the filler (F) preferably has insulating properties and does not hinder the permeability to various active energy rays used for photocuring, and has a wavelength of 365 nm (i-line) and / or a wavelength of 405 nm (h). It is more preferable that the line) does not impede the permeability to the active energy line.
- Examples of the filler (F) include silica (for example, natural silica, molten silica, amorphous silica, hollow silica, etc.), aluminum compounds (for example, boehmite, aluminum hydroxide, alumina, and aluminum nitride, etc.), and boron compounds.
- silica for example, natural silica, molten silica, amorphous silica, hollow silica, etc.
- aluminum compounds for example, boehmite, aluminum hydroxide, alumina, and aluminum nitride, etc.
- boron compounds for example, boron nitride, etc.
- magnesium compounds for example, magnesium oxide, magnesium hydroxide, etc.
- calcium compounds for example, calcium carbonate, etc.
- molybdenum compounds for example, molybdenum oxide, zinc molybdate, etc.
- fillers (F) can be used alone or in admixture of two or more.
- silica boehmite, barium sulfate, silicone powder, fluororesin-based filler, urethane resin-based filler, (meth) acrylic resin-based filler, polyethylene-based filler, styrene-butadiene rubber, and silicone rubber. It is preferably one or more selected from the group.
- These fillers (F) may be surface-treated with a silane coupling agent or the like described later.
- Silica is preferable, and molten silica is more preferable, from the viewpoint of improving the heat resistance of the cured product and obtaining good coating film properties.
- Specific examples of silica include SFP-130MC (trade name) manufactured by Denka Co., Ltd., SC2050-MB (trade name) manufactured by Admatex Co., Ltd., SC1050-MLE (trade name), and YA010C-MFN (trade name). ), And YA050C-MJA (trade name).
- the particle size of the filler (F) is not particularly limited, but is usually 0.005 to 10 ⁇ m, preferably 0.01 to 1.0 ⁇ m, from the viewpoint of ultraviolet light transmission of the resin composition.
- the content of the filler (F) is the content of the bismaleimide compound (A) and the maleimide compound (B) from the viewpoint of improving the light transmittance of the resin composition and the heat resistance of the cured product. It is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 100 parts by mass or less with respect to 100 parts by mass in total.
- the lower limit is 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B) from the viewpoint of obtaining the effect of improving various properties such as coating film property and heat resistance. However, it is usually 1 part by mass.
- silane coupling agent and wet dispersant In the resin composition of the present embodiment, a silane coupling agent and / or a wet dispersant can be used in combination in order to improve the dispersibility of the filler and the adhesive strength between the polymer and / or the resin and the filler. ..
- These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment of inorganic substances.
- mercaptosilane series such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane
- ureidosi such as 3-ureidopropyltriethoxysilane Orchid type
- Styrylsilane type such as p-styryltrimethoxysilane
- Cationic silane type such as N- ⁇ - (N-vinylbenzylaminoethyl- ⁇ -aminopropyltrimethoxysilane hydrochloride; [3- (trimethoxysilyl) ) Procyl] Acid anhydrides such as succinic anhydride
- phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane
- trimethoxy Examples
- the content of the silane coupling agent is usually 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- the wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include, for example, DISPERBYK (registered trademark) -110 (trademark), 111 (product name), 118 (product name), 180 (product name), 161 (product name) manufactured by Big Chemie Japan Co., Ltd. , BYK®-W996 (trade name), W9010 (trade name), and W903 (trade name). These wet dispersants can be used alone or in admixture of two or more. In the resin composition, the content of the wet dispersant is usually 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- the bismaleimide compound (A), the maleimide compound (B), and light are used according to the properties such as flame retardancy, heat resistance, and thermal expansion characteristics of the cured product.
- the compound (D) containing one or more carboxy groups, and the maleimide compound (E), a cyanate ester compound, a phenol resin, an oxetane resin, a benzoxazine compound, an epoxy resin, and other compounds are Various kinds of compounds and resins can be used.
- the resin composition is exposed to light and photocures. It is preferable to do so.
- active energy rays containing a wavelength of 365 nm (i line) and / or active energy rays containing 405 nm (h line) the resin composition is exposed to light and photocures. It is preferable to do so.
- These compounds and resins can be used alone or in admixture of two or more.
- the cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety in the molecule in which at least one cyanato group (cyanic acid ester group) is substituted.
- Ar 1 represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. When there are a plurality of them, they may be the same or different from each other.
- Ra independently has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and 1 carbon group. Indicates a group in which an alkyl group of ⁇ 6 and an aryl group having 6 to 12 carbon atoms are bonded.
- the aromatic ring in Ra may have a substituent, and the substituent in Ar 1 and Ra can be selected at any position.
- p indicates the number of cyanato groups attached to Ar 1 , and each is an integer of 1 to 3 independently.
- q represents the number of Ra to bind to Ar 1, the 4-p when Ar 1 is a benzene ring, when the naphthalene ring when those 6-p, 2 one benzene ring is a single bond is 8-p .
- t indicates the average number of repetitions and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds having different t.
- each of them is independently a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be substituted with a hetero atom), and a divalent group having 1 to 10 nitrogen atoms.
- Organic group for example, -N-RN-, where R indicates an organic group
- the alkyl group in Ra of the formula (26) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group). Further, the hydrogen atom in the alkyl group in the formula (26) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom and a chlorine atom, an alkoxyl group such as a methoxy group and a phenoxy group, or a cyano group. You may.
- alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group and 2,2-dimethylpropyl group.
- alkyl group examples include a group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group and the like.
- alkenyl group examples include a vinyl group, a (meth) allyl group, an isopropenyl group, a 1-propenyl group, a 2-butenyl group, a 3-butenyl group, a 1,3-butandienyl group, and a 2-methyl-2-propenyl group.
- 2-Pentenyl group 2-hexenyl group and the like.
- aryl group examples include phenyl group, xsilyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group and trifluorophenyl.
- Groups, methoxyphenyl groups, o-, m- or p-tolyl groups and the like can be mentioned.
- alkoxyl group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like.
- divalent organic group having 1 to 50 carbon atoms in X of the formula (26) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group and a biphenylylmethylene group.
- examples thereof include a group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorinatedyl group, a phthalidodiyl group and the like.
- the hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom and a chlorine atom, an alkoxyl group such as a methoxy group and a phenoxy group, and a cyano group.
- a halogen atom such as a fluorine atom and a chlorine atom
- an alkoxyl group such as a methoxy group and a phenoxy group
- cyano group examples include an imino group and a polyimide group.
- examples of the organic group of X in the formula (26) include those having a structure represented by the formula (27) and those having a structure represented by the formula (28).
- Ar 2 represents a benzenediyl group, a naphthalenediyl group, or a biphenyldiyl group, and when u is an integer of 2 or more, they may be the same or different from each other.
- Rb, Rc, Rf, and Rg each independently have at least one hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or a phenolic hydroxy group. Indicates an aryl group.
- Rd and Re are independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a hydroxy group.
- u represents an integer from 0 to 5.
- Ar 3 represents a benzenediyl group, a naphthalenediyl group, or a biphenyldiyl group, and when v is an integer of 2 or more, they may be the same or different from each other.
- Ri and Rj are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, benzyl groups, alkoxyl groups having 1 to 4 carbon atoms, hydroxy groups, and trifluoromethyl groups. , Or an aryl group in which at least one cyanato group is substituted.
- v represents an integer of 0 to 5, it may be a mixture of compounds in which v is different.
- z represents an integer of 4 to 7.
- Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- Ar 2 of the formula (27) and Ar 3 of the formula (28) two carbon atoms represented by the formula (27) or two oxygen atoms represented by the formula (28) are 1,4.
- Benzene diyl group bonded to the position or 1,3 position, two carbon atoms or two oxygen atoms at the 4,4'position, 2,4'position, 2,2'position, 2,3'position, 3 , 3'-position, or 3,4'-position-bonded biphenyldiyl group, and two carbon atoms or two oxygen atoms at the 2,6, 1,5, 1,6, 1, Examples thereof include a naphthalenediyl group bonded to the 8-position, 1,3-position, 1,4-position, or 2,7-position.
- the alkyl and aryl groups in Rb, Rc, Rd, Re, Rf, and Rg of formula (27) and Ri and Rj of formula (28) are synonymous with those in formula (26).
- cyanato-substituted aromatic compound represented by the formula (26) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1-cyanato. -2-, 1-Cyanato-3-, or 1-Cyanato-4-methoxybenzene, 1-Cyanato-2,3-, 1-Cyanato-2,4-, 1-Cyanato-2,5-, 1- Cianato-2,6-, 1-Cyanato-3,4- or 1-Cyanato-3,5-dimethylbenzene, Cyanatoethylbenzene, Cyanatobutylbenzene, Cyanatooctylbenzene, Cyanatononylbenzene, 2- (4) -Cianaphenyl) -2-phenylpropane (cyanate of 4- ⁇ -cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyana
- cyanate ester compounds can be used alone or in admixture of two or more.
- a phenol novolac resin and a cresol novolak resin by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde and the like, etc.
- Formaldehyde compound reacted in an acidic solution trisphenol novolak resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorennovolak resin (fluorenone compound and 9,9-bis) (hydroxyaryl) that the fluorenes were reacted in the presence of an acid catalyst), phenol aralkyl resins, cresol aralkyl resin, naphthol aralkyl resin, and biphenyl aralkyl resin (by known methods, Ar 4 - (CH 2 Y ) 2 (Ar 4 indicates a phenyl group and Y indicates a halogen atom. The same shall apply hereinafter in this paragraph).
- a hydroxy-substituted aromatic compound reacted in the presence of an acidic catalyst a phenol-modified dicyclopentadiene resin, or a phenol resin having a polynaphthylene ether structure (by a known method, a phenolic hydroxy group is contained in one molecule.
- Phenolic resins such as those obtained by dehydrating and condensing a polyvalent hydroxynaphthalene compound having two or more of them in the presence of a basic catalyst) are cyanated by the same method as described above, and these prepolymers and the like are Can be mentioned. These cyanate ester compounds may be used alone or in admixture of two or more.
- the method for producing these cyanate ester compounds is not particularly limited, and known methods can be used. Specific examples include a method in which a hydroxy group-containing compound having a desired skeleton is obtained or synthesized, and the hydroxy group is modified by a known method to cyanate. Examples of the method for cyanating a hydroxy group include the methods described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins", and "Blackie Academic & Professional".
- the cured product using these cyanate ester compounds has excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.
- the content of the cyanate ester compound is usually 0.01 to 40 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- phenol resin generally known phenol resins can be used as long as they have two or more hydroxyl groups in one molecule.
- phenol resin generally known phenol resins can be used as long as they have two or more hydroxyl groups in one molecule.
- bisphenol A type phenol resin bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl.
- the content of the phenol resin is usually 0.01 to 40 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- oxetane resin As the oxetane resin, generally known ones can be used. For example, alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoro).
- These oxetane resins can be used alone or in admixture of two or more.
- the content of the oxetane resin is usually 0.01 to 40 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- benzoxazine compound a generally known compound can be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule.
- bisphenol A type benzoxazine BA-BXZ manufactured by Konishi Chemical Industry Co., Ltd., trade name
- Bisphenol F type benzoxazine BF-BXZ manufactured by Konishi Chemical Industry Co., Ltd., trade name
- bisphenol S type benzoxazine BS- BXZ manufactured by Konishi Chemical Industry Co., Ltd., trade name
- phenolphthaline type benzoxazine and the like can be mentioned.
- These benzoxazine compounds may be used alone or in admixture of two or more.
- the content of the benzoxazine compound is usually 0.01 to 40 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- the epoxy resin is not particularly limited, and generally known ones can be used.
- the epoxy resin a commercially available product can be used.
- the epoxy resin represented by the formula (29) NC-3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd.
- n 5 in the formula (29) n 5 is about.
- a naphthalene type epoxy resin represented by the formula (30) HP-4710 (trade name) manufactured by DIC Corporation.
- epoxy resins can be used alone or in admixture of two or more.
- the content of the epoxy resin is usually 0.01 to 40 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- ⁇ Other compounds> Other compounds include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; triallyl isocyanurate, trimetaallyl. Examples thereof include isocyanurate and bisallyl nadiimide. These compounds may be used alone or in admixture of two or more. In the resin composition, the content of the other compound is usually 0.01 to 40 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether
- styrenes such as sty
- the resin composition of the present embodiment may contain an organic solvent, if necessary.
- an organic solvent When an organic solvent is used, the viscosity of the resin composition at the time of preparation can be adjusted.
- the type of the organic solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition.
- organic solvents include halogen solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotonic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, and acetonitrile; acetone, methylethylketone, and the like.
- Ketone solvents such as methylisobutylketone, cyclopentanone, and cyclohexanone; cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; phenol, and Aromatic group-containing phenol solvents such as cresol; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, ⁇ -butyrolactone, and propylene glycol monomethyl ether acetate; Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene.
- a photopolymerization initiator (C) and a compound (D) containing one or more carboxyl groups are preferable because they can exhibit excellent solubility and therefore it is easy to prepare a varnish having good solubility.
- organic solvents may be used alone or in admixture of two or more.
- the resin composition of the present embodiment contains various high molecular weight resins such as thermosetting resins, thermoplastic resins, and oligomers thereof, which have not been mentioned so far, as long as the characteristics of the present embodiment are not impaired.
- Molecular compounds; flame-retardant compounds not listed so far; additives and the like can be used in combination. These are not particularly limited as long as they are generally used.
- flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine; oxazine ring-containing compounds; phosphate compounds of phosphorus compounds, aromatic condensed phosphoric acid esters, and phosphorus-based compounds such as halogen-containing condensed phosphoric acid esters. Can be mentioned.
- Additives include UV absorbers, antioxidants, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, brighteners, polymerization inhibitors, and heat. Examples include a curing accelerator. These components may be used alone or in admixture of two or more. In the resin composition, the content of the other components is usually 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the bismaleimide compound (A) and the maleimide compound (B).
- the resin composition of the present embodiment includes a bismaleimide compound (A), a maleimide compound (B), a photocuring initiator (C) if necessary, a compound (D) containing one or more carboxy groups, and a maleimide compound ( It can be prepared by appropriately mixing E), filler (F), other resin, other compounds, additives and the like.
- Examples of the method for producing the resin composition include a method in which each of the above-mentioned components is sequentially blended with a solvent and sufficiently stirred.
- the resin composition of the present embodiment contains at least a bismaleimide compound (A) and a maleimide compound (B), and has good solubility in an organic solvent.
- the varnish obtained from the resin composition has an appropriate viscosity and a small amount of liquid components. Therefore, the resin sheet obtained by drying the varnish has good photocurability and alkali developability, and tacks the varnish. The sex is well suppressed.
- the organic solvent used for preparing the varnish is not particularly limited, and specific examples thereof are as described above.
- a known treatment for uniformly dissolving or dispersing each component can be performed.
- each component such as the bismaleimide compound (A) and the maleimide compound (B) is dispersed in the resin composition.
- the sex can be improved.
- the stirring, mixing, and kneading treatment can be performed by, for example, a stirring device for dispersing an ultrasonic homogenizer, a device for mixing three rolls, a ball mill, a bead mill, a sand mill, or a revolution or rotation type.
- an organic solvent can be used if necessary.
- the type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.
- the resin composition can be suitably used as a varnish when producing the resin sheet of the present embodiment described later.
- the varnish can be obtained by a known method.
- 10 to 900 parts by mass, preferably 30 to 500 parts by mass of the organic solvent is added to 100 parts by mass of the component excluding the organic solvent in the resin composition, and the above-mentioned known mixing treatment (stirring, stirring, And kneading treatment, etc.).
- this mixing treatment is preferably performed at a temperature of 30 to 120 ° C., and 40 to 40 to 120 ° C. More preferably, it is carried out at a temperature of 100 ° C.
- the mixing treatment time is usually 1 to 30 minutes.
- the resin composition of the present embodiment can be used for applications in which an insulating resin composition is required, and is not particularly limited.
- the resin composition is excellent in solubility, photocurability and alkali developability, and when used for a resin sheet and a printed wiring board, tackiness is suitably suppressed. Therefore, the multi-layer printed wiring is provided. It can be suitably used for an insulating layer of a plate or for a solder resist.
- the cured product is obtained by curing the resin composition.
- the cured product can be obtained, for example, by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using light.
- the wavelength region of light is preferably cured in the range of 100 to 500 nm, which is efficiently cured by a photopolymerization initiator or the like.
- the resin sheet of the present embodiment is a resin sheet with a support having a support and resin layers arranged on one side or both sides of the support, and the resin layer contains the resin composition of the present embodiment. is there.
- the resin sheet can be produced by applying the resin composition on the support and drying it.
- the resin layer in the resin sheet has well-suppressed tackiness, and has excellent photocurability and alkali developability.
- a known support can be used, and the support is not particularly limited, but is preferably a resin film.
- the resin film include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, a polyethylene (PE) film, a polyethylene naphthalate film, and a polyvinyl alcohol.
- PET film is preferable.
- the resin film is preferably coated with a release agent on the surface in order to facilitate peeling from the resin layer.
- the thickness of the resin film is preferably in the range of 5 to 100 ⁇ m, more preferably in the range of 10 to 50 ⁇ m. If the thickness is less than 5 ⁇ m, the support tends to be torn easily when the support is peeled off before alkaline development, and if the thickness exceeds 100 ⁇ m, the resolution when exposed from above the support tends to decrease. There is.
- the resin film has excellent transparency.
- the resin layer may be protected by a protective film.
- a protective film By protecting the resin layer side with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin layer and scratches. Further, since the resin layer has photocurability and alkali developability, and the tackiness is well suppressed, the protective film can be easily peeled off after the resin layer is cured.
- the protective film a film made of the same material as the resin film can be used.
- the thickness of the protective film is preferably in the range of 1 to 50 ⁇ m, more preferably in the range of 5 to 40 ⁇ m.
- the protective film preferably has a smaller adhesive force between the resin layer and the protective film than the adhesive force between the resin layer and the support.
- Examples of the method for producing a resin sheet include a method for producing a resin sheet by applying a resin composition to a support such as a PET film and drying the resin sheet to remove an organic solvent.
- the coating method can be carried out by a known method using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, a squeeze coater or the like. Drying can be performed, for example, by heating in a dryer at 60 to 200 ° C. for 1 to 60 minutes.
- the amount of the organic solvent remaining in the resin layer is preferably 5% by mass or less with respect to the total mass of the resin layer from the viewpoint of preventing the diffusion of the organic solvent in a later step.
- the thickness of the resin layer is preferably 1 to 50 ⁇ m from the viewpoint of improving handleability.
- the resin sheet can be used for manufacturing the insulating layer of the multilayer printed wiring board.
- the multilayer printed wiring board of the present embodiment has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment.
- the insulating layer can also be obtained, for example, by stacking one or more resin sheets and curing them.
- the number of layers of the insulating layer and the conductor layer can be appropriately set according to the intended use. Further, the order of the insulating layer and the conductor layer is not particularly limited.
- the conductor layer may be a metal foil used for various printed wiring board materials, and examples thereof include metal foils such as copper and aluminum. Examples of the copper metal foil include rolled copper foil and copper foil such as electrolytic copper foil.
- the thickness of the conductor layer is usually 1 to 100 ⁇ m. Specifically, it can be produced by the following method.
- the resin layer side of the resin sheet is laminated on one side or both sides of the circuit board using a vacuum laminator.
- the circuit board include a glass epoxy board, a metal substrate, a ceramic substrate, a silicon substrate, a semiconductor encapsulating resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermocurable polyphenylene ether substrate.
- the circuit board refers to a board on which a patterned conductor layer (circuit) is formed on one side or both sides of the board as described above.
- a circuit board is also a circuit board in which one or both sides of the outermost layer of the multi-layer printed wiring board is a patterned conductor layer (circuit).
- the insulating layer laminated on the multilayer printed wiring board may be an insulating layer obtained by stacking one or more resin sheets of the present embodiment and curing the resin sheet of the present embodiment.
- the insulating layer may be obtained by stacking one or more of each of the resin sheet of the embodiment and a known resin sheet different from the present embodiment.
- the method of stacking the resin sheet of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment is not particularly limited.
- the surface of the conductor layer may be roughened in advance by blackening treatment and / or copper etching or the like.
- the protective film is peeled off and removed, and then the resin sheet and the circuit board are preheated as necessary, and the resin layer of the resin sheet is pressurized and heated. While crimping to the circuit board.
- a method of laminating a resin layer of a resin sheet on a circuit board under reduced pressure by a vacuum laminating method is preferably used.
- the conditions of the laminating process are, for example, a crimping temperature (lamination temperature) of 50 to 140 ° C., a crimping pressure of 1 to 15 kgf / cm 2 , a crimping time of 5 to 300 seconds, and an air pressure of 20 mmHg or less under reduced pressure. It is preferable to laminate. Further, the laminating step may be a batch type or a continuous type using a roll.
- the vacuum laminating method can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a two-stage build-up laminator manufactured by Nikko Materials Co., Ltd.
- the exposure step After the resin layer is provided on the circuit board by the laminating step, a predetermined portion of the resin layer is irradiated with active energy rays as a light source to cure the resin layer of the irradiated portion.
- the tackiness of the obtained resin layer is preferably suppressed.
- the compound (D) does not inhibit the photocuring reaction in the exposure step. Irradiation may be performed through a mask pattern, or a direct drawing method of direct irradiation may be used.
- the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like.
- the wavelength of the active energy ray is, for example, in the range of 200 to 600 nm.
- the irradiation amount is about 10 to 1000 mJ / cm 2 .
- an active energy ray having a wavelength of 365 nm (i-line) is used as the active energy ray. Is preferable.
- the irradiation amount thereof is approximately 10 to 10,000 mJ / cm 2 .
- an active energy ray containing a wavelength of 405 nm (h line) is used as the active energy ray.
- the irradiation amount thereof is approximately 10 to 10,000 mJ / cm 2 .
- the exposure method through which the mask pattern is passed includes a contact exposure method in which the mask pattern is brought into close contact with a multilayer printed wiring board and a non-contact exposure method in which the mask pattern is exposed using parallel rays without being brought into close contact with each other. It doesn't matter.
- the support is present on the resin layer, it may be exposed from above the support, or the support may be exposed after peeling.
- Alkaline development process When the support is not present on the resin layer, after the exposure step, the non-photocured portion (unexposed portion) is directly removed by alkaline development and developed to form an insulating layer pattern. can do.
- the support is removed after the exposure step, and then the non-photocured portion (unexposed portion) is removed by alkaline development and developed. Thereby, the pattern of the insulating layer can be formed. Since the unexposed resin layer containing the resin composition of the present embodiment has excellent alkali developability, a printed wiring board having a high-definition pattern can be obtained.
- the developer is not particularly limited as long as it selectively elutes the unexposed portion, but is an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of sodium hydroxide, and the like.
- An alkaline developer such as an aqueous potassium hydroxide solution is used. In this embodiment, it is more preferable to use an aqueous solution of tetramethylammonium hydroxide.
- These alkaline developers can be used alone or in admixture of two or more.
- the alkaline development method for example, a known method such as dipping, paddle, spraying, rocking dipping, brushing, and scraping can be performed. In pattern formation, these developing methods may be used in combination, if necessary. Further, as a developing method, it is preferable to use a high-pressure spray because the resolution is further improved. When the spray method is adopted, the spray pressure is preferably 0.02 to 0.5 MPa.
- a post-baking step is performed to form an insulating layer (cured product).
- the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp and a heating step using a clean oven, and these can also be used in combination.
- the irradiation amount can be adjusted as needed, and for example, irradiation can be performed at an irradiation amount of about 0.05 to 10 J / cm 2.
- the heating conditions can be appropriately selected as needed, but are preferably selected in the range of 150 to 220 ° C. for 20 to 180 minutes, and more preferably in the range of 160 to 200 ° C. for 30 to 150 minutes.
- a conductor layer is formed on the surface of the insulating layer by dry plating.
- the surface of the insulating layer may be surface-modified before the dry plating.
- known methods such as plasma etching treatment, reverse sputtering treatment, and corona treatment can be used.
- the dry plating known methods such as a thin film deposition method, a sputtering method, and an ion plating method can be used.
- a metal film can be formed on an insulating layer by placing a multilayer printed wiring board in a vacuum vessel and heating and evaporating the metal.
- a multilayer printed wiring board is placed in a vacuum vessel, an inert gas such as argon is introduced, a DC voltage is applied, and the ionized inert gas collides with a target metal and is beaten out.
- a metal film can be formed on the insulating layer by the metal.
- a conductor layer is formed by electroless plating or electrolytic plating.
- a method for forming a pattern thereafter for example, a subtractive method, a semi-additive method, or the like can be used.
- the semiconductor device of this embodiment includes the resin composition of this embodiment. Specifically, it can be produced by the following method.
- a semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of a multilayer printed wiring board.
- the conductive portion is a portion of the multilayer printed wiring board that transmits an electric signal, and the location may be a surface or an embedded portion.
- the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
- the mounting method of the semiconductor chip when manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, and a non-conductive film (NCF) mounting method. And so on.
- a semiconductor device can also be manufactured by forming an insulating layer containing a resin composition on a semiconductor chip or a substrate on which the semiconductor chip is mounted.
- the shape of the substrate on which the semiconductor chip is mounted may be wafer-shaped or panel-shaped. After the formation, it can be manufactured by the same method as the above-mentioned multilayer printed wiring board.
- MIZ-001 (trade name, mass average molecular weight (Mw): 3000) manufactured by Nippon Kayaku Co., Ltd. is used as the bismaleimide compound (A), and this MIZ-001 (trade name) is contained in 1% by mass.
- a chloroform solution was prepared, and the transmittances at wavelengths of 365 nm and 405 nm were measured using a UV-vis measuring device (Hitachi spectrophotometer U-4100 (trade name) manufactured by Hitachi High-Technologies Corporation). ..
- the photo-curing initiator (C) bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins BV) is used.
- Omnirad® 819 trade name
- UV-vis measuring device U-4100 (trade name)
- cis-4-cyclohexene-1,2-dicarboxylic acid anhydride manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight: 152
- a UV-vis measuring device (Hitachi spectrophotometer U-4100 manufactured by Hitachi High-Technologies Co., Ltd.) was prepared by preparing an N-methylpyrrolidone solution containing 1% by mass of -1,2-dicarboxylic acid anhydride (trade name). was used to measure the transmittances at wavelengths of 365 nm and 405 nm, respectively. The results are shown in Table 1.
- 6-amino-1,3,3-trimethyl-1-indan and 6-amino-1,3,3-trimethyl-1-indan were added to this solution.
- 5.0 g (19 mmol) of a mixture of (4-aminophenyl) -indane) and 10 mL of NMP were added, and the mixture was stirred at room temperature (25 ° C.) for 17 hours.
- a part of the reaction solution was taken, water and ethyl acetate were added, and the mixture was shaken. Then, the organic layer was taken out and dried over magnesium sulfate. The supernatant was solvent distilled off at 40 ° C. to obtain a yellow oil.
- Example 1 (Preparation of resin composition and resin sheet)
- MIZ-001 (trade name) is 60 parts by mass
- maleimide compound (B) BCPH13 (trade name) manufactured by Gunei Chemical Industry Co., Ltd. is 25 parts by mass
- maleimide compound As (B), 15 parts by mass of TMDM, and as the photocuring initiator (C), 5 of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Omnirad (registered trademark) 819 (trade name)).
- compound (D) containing one or more parts by mass and one or more carboxy groups cis-4-cyclohexene-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to 10 parts by mass as an organic solvent. 168.8 parts by mass of methyl ethyl ketone (manufactured by Idemitsu Kosan Co., Ltd.) was mixed and stirred in a hot water bath at 90 ° C. to obtain a varnish (resin composition).
- the resin surface of the obtained resin sheet is placed on the copper surface (one side) on the inner layer circuit board, and evacuated for 30 seconds (5.0 hPa or less) using a vacuum laminator (manufactured by Nikko Materials Co., Ltd.). ), Then laminating molding was performed at a pressure of 10 kgf / cm 2 and a temperature of 70 ° C. for 30 seconds. Further, laminating molding was performed at a pressure of 10 kgf / cm 2 and a temperature of 70 ° C. for 60 seconds to obtain an evaluation laminate in which the inner layer circuit board, the resin layer and the support were laminated.
- Example 2 As the bismaleimide compound (A), 50 parts by mass of MIZ-001 (trade name) was used instead of 60 parts by mass of MIZ-001 (trade name), and as the maleimide compound (B), TMDM25 was used instead of 15 parts by mass of TMDM. A varnish and a resin sheet were obtained in the same manner as in Example 1 except that parts by mass were used. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 3 As the bismaleimide compound (A), 55 parts by mass of MIZ-001 (trade name) was used instead of 60 parts by mass of MIZ-001 (trade name), and as the maleimide compound (B), TMDM20 was used instead of 15 parts by mass of TMDM. A varnish and a resin sheet were obtained in the same manner as in Example 1 except that parts by mass were used. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 4 As the bismaleimide compound (A), 65 parts by mass of MIZ-001 (trade name) was used instead of 60 parts by mass of MIZ-001 (trade name), and as the maleimide compound (B), TMDM10 was used instead of 15 parts by mass of TMDM. A varnish and a resin sheet were obtained in the same manner as in Example 1 except that parts by mass were used. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 5 Example 1 and Example 1 except that as the maleimide compound (B), 15 parts by mass of BMI-70 (trade name) manufactured by KI Kasei Co., Ltd. represented by the formula (20) was used instead of 15 parts by mass of TMDM. In the same manner, a varnish and a resin sheet were obtained. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 6 Example 1 and Example 1 except that as the maleimide compound (B), 15 parts by mass of BMI-80 (trade name) manufactured by KI Kasei Co., Ltd. represented by the formula (21) was used instead of 15 parts by mass of TMDM. In the same manner, a varnish and a resin sheet were obtained. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 7 Same as Example 1 except that 15 parts by mass of BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. represented by the formula (22) was used as the maleimide compound (B) instead of 15 parts by mass of TMDM. Then, a varnish and a resin sheet were obtained. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 8 As the maleimide compound (B), instead of 25 parts by mass of BCPH13 (trade name) manufactured by Gun Ei Chemical Industry Co., Ltd., MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. represented by the formula (18). A varnish and a resin sheet were obtained in the same manner as in Example 1 except that 25 parts by mass was used. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 9 Example 8 and Example 8 except that 15 parts by mass of BMI-70 (trade name) manufactured by KI Kasei Co., Ltd. represented by the formula (20) was used as the maleimide compound (B) instead of 15 parts by mass of TMDM. In the same manner, a varnish and a resin sheet were obtained. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 10 Example 8 and Example 8 except that 15 parts by mass of BMI-80 (trade name) manufactured by KI Kasei Co., Ltd. represented by the formula (21) was used as the maleimide compound (B) instead of 15 parts by mass of TMDM. In the same manner, a varnish and a resin sheet were obtained. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 11 Same as Example 8 except that 15 parts by mass of BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. represented by the formula (22) was used as the maleimide compound (B) instead of 15 parts by mass of TMDM. Then, a varnish and a resin sheet were obtained. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 12 Example 1 and Example 1 except that, as the photo-curing initiator (C), 5 parts by mass of Omnirad (registered trademark) 819 (trademark) was used instead of 5 parts by mass of Omnirad (registered trademark) 369 (trademark).
- a varnish and a resin sheet were obtained.
- an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 13 Example 1 and Example 1 except that, as the photo-curing initiator (C), 5 parts by mass of Omnirad (registered trademark) 819 (trade name) was used instead of 5 parts by mass of Omnirad (registered trademark) 907 (trade name).
- a varnish and a resin sheet were obtained.
- an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 1 As a bismaleimide compound, MIZ-001 (trade name) is 60 parts by mass, as a photocuring initiator, Omnirad (registered trademark) 819 (trade name) is 5 parts by mass, and as a compound containing one or more carboxy groups. Mix 112.5 parts by mass of methyl ethyl ketone as an organic solvent with 10 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and in a hot water bath at 90 ° C. The mixture was stirred to obtain a varnish (resin composition). Using this varnish, a resin sheet was obtained in the same manner as in Example 1. Further, using this resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- MIZ-001 (trade name) is 60 parts by mass
- BCPH13 (trade name) manufactured by Gunei Chemical Industry Co., Ltd. is 25 parts by mass
- Omnirad (trade name) is used as a photocuring initiator. 10 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) as a compound containing 5 parts by mass of registered trademark) 819 (trade name) and one or more carboxy groups.
- Example 1 150 parts by mass of methyl ethyl ketone was mixed with respect to the parts as an organic solvent, and the mixture was stirred in a hot water bath at 90 ° C. to obtain a varnish (resin composition). Using this varnish, a resin sheet was obtained in the same manner as in Example 1. Further, using this resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Comparative Example 3 A varnish and a resin sheet were obtained in the same manner as in Comparative Example 2 except that BCPH13 (trade name) manufactured by Gun Ei Chemical Industry Co., Ltd. was used as a maleimide compound in an amount of 15 parts by mass instead of 25 parts by mass of TMDM. .. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 6 As the maleimide compound, 50 parts by mass of MIZ-001 (trade name) was used instead of 60 parts by mass of MIZ-001 (trade name), and as the maleimide compound, TMDM was used instead of 15 parts by mass by the formula (34). Represented Designer Moleculars Inc. A varnish and a resin sheet were obtained in the same manner as in Example 1 except that 25 parts by mass of BMI-6100 manufactured by BMI-6100 (trade name, in formula (34), x is 18 and y is 18) was used. It was. Further, using the resin sheet, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Photo DSC (TA Instruments Japan Co., Ltd.) with a light source capable of irradiating active energy rays with a wavelength of 200 to 600 nm (Omnicure (registered trademark) S2000 (trade name) manufactured by Uvix Co., Ltd.)
- DSC-2500 (trade name) manufactured by DSC-2500 (trade name)
- the obtained evaluation resin is irradiated with an active energy ray containing a wavelength of 200 to 600 nm at an illuminance of 30 mW and an exposure time of 3.5 minutes, and the horizontal axis is time (sec). ),
- the vertical axis is the heat flow (mW) graph.
- the horizontal axis is time (sec) and the vertical axis is vertical, except that an active energy ray having a wavelength of 405 nm (h line) is used as a light source using a filter having a wavelength of 405 nm (h line).
- a graph of heat flow (mW) on the axis was obtained.
- the peak area when a horizontal line was drawn from the end point of the graph was defined as enthalpy (J / g). Curability was evaluated according to the following criteria. "AA”: The enthalpy was 1 (J / g) or more.
- ⁇ Tackiness> In the obtained resin sheet, the tackiness was evaluated according to the following criteria based on the height at which the support was lifted when the finger was pressed against the resin surface and held for 1 second, and then the finger was lifted. "AA”: The height at which the support was lifted was less than 1 cm from the reference plane. "CC”: The height at which the support was lifted was 1 cm or more from the reference plane.
- the obtained evaluation laminate is irradiated from above the support using a light source (MA-20 (trade name) manufactured by Mikasa Co., Ltd.) capable of irradiating an active energy ray containing a wavelength of 405 nm (h line). Irradiation was performed at an amount of 200 mJ / cm 2 , half of the resin layer was exposed, and the rest was unexposed. Then, the support (PET film) was peeled off and shaken in a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution (developing solution, manufactured by Tokuyama Corporation) for 90 seconds.
- TMAH tetramethylammonium hydroxide
- FIG. 3 shows photographs after alkaline development performed using the respective resin sheets obtained in Example 1 and Comparative Example 6.
- a varnish having good solubility can be obtained.
- the resin composition of the present embodiment is satisfactorily exposed to light when exposed to either an active energy ray containing 405 nm (h line) or an active energy ray containing a wavelength of 200 to 600 nm, and photocuring is performed. It is possible. And, in the unexposed part, it has excellent alkali developability.
- the resin composition of the present embodiment is industrially useful because it has good solubility and photocurability, and is a photosensitive film, a photosensitive film with a support, a prepreg, a resin sheet, and a circuit board (used for laminated boards). , And multi-layer printed wiring board applications, etc.), solder resist, underfill material, die bonding material, semiconductor encapsulant, hole filling resin, component embedding resin, etc.
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Abstract
Description
一方、本発明者らは、マレイミド化合物を含み、溶解性に優れるワニスは、液状成分が多いため、乾燥しても、得られる樹脂シートは、タック性が強いとの知見を得た。
[1]下記式(1)で表される構成単位と、分子鎖の両末端にマレイミド基と、を含む、ビスマレイミド化合物(A)と、下記式(2)で表される化合物、下記式(3)で表される化合物、下記式(4)で表される化合物、下記式(5)で表される化合物、下記式(6)で表される化合物、及び下記式(7)で表される化合物からなる群より選択される少なくとも2種のマレイミド化合物(B)と、を含む、樹脂組成物。
[3]前記光硬化開始剤(C)が、下記式(8)で表される化合物を含む、[2]に記載の樹脂組成物。
[5]前記カルボキシ基を1つ以上含む化合物(D)が、下記式(10)で表される化合物、下記式(11)で表される化合物、下記式(12)で表される化合物、及び下記式(13)で表される化合物からなる群より選択される少なくとも1種である、[4]に記載の樹脂組成物。
[7]前記樹脂層の厚さが1~50μmである、[6]に記載の樹脂シート。
[8]絶縁層と、前記絶縁層の片面又は両面に形成された導体層と、を有し、前記導体層が、[1]~[5]のいずれかに記載の樹脂組成物を含む、多層プリント配線板。
[9][1]~[5]のいずれかに記載の樹脂組成物を含む、半導体装置。
本実施形態の樹脂組成物は、特定のビスマレイミド化合物(A)と、式(2)で表される化合物、式(3)で表される化合物、式(4)で表される化合物、式(5)で表される化合物、式(6)で表される化合物、及び式(7)で表される化合物からなる群より選択される少なくとも2種のマレイミド化合物(B)と、を含む。以下、各成分について説明する。
樹脂組成物は、ビスマレイミド化合物(A)(成分(A)とも称す)を含む。ビスマレイミド化合物(A)は、式(1)で表される構成単位と、分子鎖の両末端にマレイミド基と、を含む。
通常、マレイミド化合物は光透過性が悪いため、樹脂組成物がマレイミド化合物を含むと、樹脂組成物中に分散している光硬化開始剤まで十分に光が届かず、光硬化開始剤がラジカルを発生し難い。そのため、一般的にマレイミド化合物の光ラジカル反応は進行し難く、仮にマレイミド単体のラジカル重合や二量化反応が進行しても、その反応性は非常に低い。しかし、ビスマレイミド化合物(A)は、式(1)で表される構成単位、すなわち、脂環骨格を有するので、光透過性に非常に優れる。そのため、光硬化開始剤まで十分に光が届き、マレイミドの光ラジカル反応が効率的に起き、ビスマレイミド化合物(A)及び後述のマレイミド化合物(B)と、必要に応じて配合される、後述の光硬化開始剤(C)及び後述のカルボキシル基を1つ以上含む化合物(D)と共に、種々の活性エネルギー線を用いて光硬化させることができる。
通常、マレイミド化合物を含む樹脂組成物は、マレイミド化合物同士や、マレイミド化合物と、光重合開始剤及びカルボキシ基を1つ以上含む化合物等のその他の化合物との相溶性が悪い。そのため、有機溶媒への溶解性が悪く、このような樹脂組成物をワニス化することが難しい。一方、ワニスが、マレイミド化合物を含み、溶解性に優れるとしても、このようなワニスには液状成分が多く含まれるため、ワニスを乾燥しても、得られる樹脂シートは、タック性が強いとの問題を有する。しかし、ビスマレイミド化合物(A)と、後述の特定のマレイミド化合物(B)のうち少なくとも2種類以上とを混合して得られる樹脂組成物であれば、優れた光硬化性を有しながら、優れた相溶性を有するため、有機溶媒への溶解性が良好である。そのうえで、ワニスに用いた場合には、ワニス中において液状成分が少ないため、ワニスを乾燥して得られる樹脂シートは、タック性が良好に抑制される。
ビスマレイミド化合物(A)の式(1)中、R1は、炭素数1~16の直鎖状若しくは分岐状のアルキレン基、又は炭素数2~16の直鎖状若しくは分岐状のアルケニレン基を示す。R1としては、好適な粘度が得られ、ワニスの粘度上昇が制御できる点から、直鎖状若しくは分岐状のアルキレン基であることが好ましく、直鎖状のアルキレン基であることがより好ましい。
直鎖状若しくは分岐状のアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、2,2-ジメチルプロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、ドデシレン基、ウンデシレン基、トリデシレン基、テトラデシレン基、ペンタデシレン基、ヘキサデシレン基、ネオペンチレン基、ジメチルブチレン基、メチルヘキシレン基、エチルヘキシレン基、ジメチルヘキシレン基、トリメチルヘキシレン基、メチルヘプチレン基、ジメチルヘプチレン基、トリメチルヘプチレン基、テトラメチルヘプチレン基、エチルヘプチレン基、メチルオクチレン基、メチルノニレン基、メチルデシレン基、メチルドデシレン基、メチルウンデシレン基、メチルトリデシレン基、メチルテトラデシレン基、及びメチルペンタデシレン基が挙げられる。
直鎖状若しくは分岐状のアルケニレン基としては、例えば、ビニレン基、1-メチルビニレン基、アリレン基、プロペニレン基、イソプロペニレン基、1-ブテニレン基、2-ブテニレン基、1-ペンテニレン基、2-ペンテニレン基、イソペンチレン基、シクロペンテニレン基、シクロヘキセニレン基、及びジシクロペンタジエニレン基等が挙げられる。
直鎖状若しくは分岐状のアルキレン基としては、前記のR1が参照できる。
直鎖状若しくは分岐状のアルケニレン基としては、前記のR1が参照できる。
直鎖状若しくは分岐状のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、1-エチルプロピル基、n-ブチル基、2-ブチル基、イソブチル基、tert-ブチル基、n-ペンチル基、2-ペンチル基、tert-ペンチル基、2-メチルブチル基、3-メチルブチル基、2,2-ジメチルプロピル基、n-ヘキシル基、2-ヘキシル基、3-ヘキシル基、n-へプチル基、n-オクチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基、2-メチルペンタン-3-イル基、及びn-ノニル基が挙げられる。
直鎖状若しくは分岐状のアルケニル基としては、例えば、ビニル基、アリル基、4-ペンテニル基、イソプロペニル基、イソペンテニル基、2-ヘプテニル基、2-オクテニル基、及び2-ノネニル基が挙げられる。
マレイミド基は、式(14)で表され、N原子がビスマレイミド化合物(A)の分子鎖に結合している。また、ビスマレイミド化合物(A)に結合されるマレイミド基は、全て同一であっても異なっていてもよいが、分子鎖の両末端のマレイミド基は同一であることが好ましい。
アルキル基の炭素数としては、好適に光硬化する点から、1~3であることが好ましく、1~2であることがより好ましい。
直鎖状若しくは分岐状のアルキル基としては、前記のR3が参照できる。
ビスマレイミド化合物(A)は、公知の方法により製造することができる。例えば、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物と、ダイマージアミン等を含むジアミンを含むモノマーと、無水マレイン酸とを、通常80~250℃程度、好ましくは100~200℃程度の温度において、通常0.5~50時間程度、好ましくは1~20時間程度、重付加反応させて重付加物を得る、その後、通常60~120℃程度、好ましくは80~100℃程度の温度において、通常0.1~2時間程度、好ましくは0.1~0.5時間程度、重付加物をイミド化反応、すなわち、脱水閉環反応させることで、ビスマレイミド化合物(A)を得ることができる。
1,2,4,5-シクロヘキサンテトラカルボン酸二無水物のモル数と、ジアミンを含むモノマー及びマレイミド化合物との全量のモル数とを調製することで、任意のビスマレイミド化合物(A)を得ることができる。
触媒の添加量は、例えば、イミド化剤を、アミド基に対して、0.5~5.0倍モル当量程度、脱水触媒を、アミド基に対して、0.5~10.0倍モル当量とすることが好ましい。
本実施形態の樹脂組成物は、本実施形態に係るビスマレイミド化合物(A)以外のマレイミド化合物(B)(成分(B)とも称す)を含む。マレイミド化合物(B)は、式(2)で表される化合物、式(3)で表される化合物、式(4)で表される化合物、式(5)で表される化合物、式(6)で表される化合物、及び式(7)で表される化合物からなる群より選択される少なくとも2種である。マレイミド化合物(B)は、式(2)~(7)で表される化合物のうち、2種以上を適宜混合して使用することができる。また、樹脂組成物は、ビスマレイミド化合物(A)とマレイミド化合物(B)とがより良好な溶解性を有し、光硬化性により優れながら、ワニス中における液状成分をより少なくでき、タック性がより抑制される樹脂シートを得ることができる点から、マレイミド化合物(B)として、式(2)~(7)で表される化合物のうち、2~4種の化合物を含むことが好ましく、2種の化合物を含むことがより好ましい。
また、マレイミド化合物(B)は、ビスマレイミド化合物(A)との相溶性が良好であり、かつ、有機溶媒への優れた溶解性を有する。一方、ビスマレイミド化合物(A)と共にマレイミド化合物(B)を用いてワニスを作製した場合、マレイミド化合物(B)は、系中の液状成分の割合を好適に抑制することができるため、ワニスを乾燥して得られる樹脂シートは、タック性が良好に抑制することができる。更に、得られる硬化物は、耐熱性、絶縁信頼性、及び熱安定性に優れるため、本実施形態の樹脂組成物によれば、保護膜、及び絶縁層を好適に形成することができる。
(式(2)で表される化合物)
式(2)で表される化合物は、次の化合物である。
炭素数1~6の直鎖状若しくは分岐状のアルキル基としては、前記の式(1)中におけるR3が参照できる。アルキル基としては、溶剤に対する良好な溶解性、低融点、低吸水性、及び他の樹脂との良好な相溶性を発全する観点から、メチル基、エチル基、n-プロピル基、イソプロピル基が好ましく、メチル基であることがより好ましい。
また、R4、R5、及びR6においては、より優れた溶剤に対する溶解性を発現する観点から、R4及びR6が、炭素数1~6の直鎖状若しくは分岐状のアルキル基であり、かつ、R5が、水素原子であることが好ましい。なお、好ましいアルキル基については、前記のとおりである。
n2は、溶剤に対する溶解性に優れ、より好適な粘度が得られ、ワニスの粘度上昇がより制御できる点から、1~10の整数であることが好ましく、1~6の整数であることがより好ましい。
式(3)で表される化合物は、次の化合物である。
式(3)で表されるマレイミド化合物としては、市販品を用いてもよく、例えば、式(18)で表される日本化薬(株)社製MIR-3000(商品名)が挙げられる。
式(4)で表される化合物は、次の化合物である。
置換基を有してもよい、炭素数1~8の直鎖状若しくは分岐状のアルキル基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、n-ペンチル基、1-エチルプロピル基、2,2-ジメチルプロピル基、シクロペンチル基、ヘキシル基、及びヘプチル基等が挙げられる。これらのアルキル基中の水素原子は、フッ素原子、及び塩素原子等のハロゲン原子、並びにシアノ基等で置換されていてもよい。これらのアルキル基の中でも、光硬化性、耐熱性、及び熱安定性により優れ、並びに溶剤に対するより良好な溶解性を有する点から、メチル基、エチル基、イソプロピル基、及びtert-ブチル基であることが好ましく、メチル基、エチル基、tert-ブチル基であることがより好ましく、メチル基であることが更に好ましい。
式(4)で表される化合物としては、光硬化性、耐熱性、及び熱安定性により優れ、並びに溶剤に対するより良好な溶解性を有する点から、式(19)で表される化合物(本実施形態では、TMDMとも称す)であることが更により好ましい。
式(5)で表される化合物は、次の化合物である。
R11としては、溶剤に対する良好な溶解性、低沸点、低吸水性、及び他の樹脂との良好な相溶性を発現する観点から、メチル基、又はエチル基であることが好ましい。
R12としては、溶剤に対する良好な溶解性、低沸点、低吸水性、及び他の樹脂との良好な相溶性を発現する観点から、水素原子であることが好ましい。
式(6)で表される化合物は、次の化合物である。
R13としては、溶剤に対する良好な溶解性、低沸点、低吸水性、及び他の樹脂との良好な相溶性を発現する観点から、メチル基、又はエチル基であることが好ましい。
式(6)で表されるマレイミド化合物としては、市販品を用いてもよく、例えば、式(21)で表されケイ・アイ化成(株)製BMI-80(商品名)が挙げられる。
式(7)で表される化合物は、次の化合物である。
R14としては、溶剤に対する良好な溶解性、低沸点、低吸水性、及び他の樹脂との良好な相溶性を発現する観点の点から、水素原子であることが好ましい。
n4としては、溶剤に対する溶解性に優れ、より好適な粘度が得られ、ワニスの粘度上昇がより制御できる点から、1~5の整数であることがより好ましい。
本実施形態の樹脂組成物は、光硬化開始剤(C)(成分(C)とも称す)を更に含むことが好ましい。光硬化開始剤(C)は、特に限定されず、一般に光硬化性樹脂組成物で用いられる分野で公知のものを使用することができる。光硬化開始剤(C)は、ビスマレイミド化合物(A)、マレイミド化合物(B)、及び後述のカルボキシル基を1つ以上含む化合物(D)等と共に、種々の活性エネルギー線を用いて光硬化させるために用いられる。
p-メトキシフェニルジアゾニウムフロロホスホネート、及びN,N-ジエチルアミノフェニルジアゾニウムヘキサフロロホスホネート等のルイス酸のジアゾニウム塩;ジフェニルヨードニウムヘキサフロロホスホネート、及びジフェニルヨードニウムヘキサフロロアンチモネート等のルイス酸のヨードニウム塩;トリフェニルスルホニウムヘキサフロロホスホネート、及びトリフェニルスルホニウムヘキサフロロアンチモネート等のルイス酸のスルホニウム塩;トリフェニルホスホニウムヘキサフロロアンチモネート等のルイス酸のホスホニウム塩;その他のハロゲン化物;トリアジン系開始剤;ボーレート系開始剤;その他の光酸発生剤等のカチオン系光重合開始剤が挙げられる。
これらの光硬化開始剤(C)は、1種単独又は2種以上を適宜混合して使用することも可能である。
式(9)中、R16は、各々独立に、水素原子又はメチル基を表す。R16のうち、1つ以上がメチル基であることが好ましく、全てメチル基であることがより好ましい。
本実施形態の樹脂組成物は、カルボキシル基を1つ以上含む化合物(D)(成分(D)又は化合物(D)とも称す)を更に含むことが好ましい。化合物(D)は、化合物中に、カルボキシ基を1つ以上含めば、特に限定されない。カルボキシ基は、ナトリウム塩、及びカリウム塩などの塩であってもよく、分子内にカルボキシ基を2以上含む場合には、それらが互いに連結して形成された酸無水物であってもよい。化合物(D)は、1種単独又は2種以上を適宜混合して使用することも可能である。
化合物(D)は、1質量%で含まれるN-メチルピロリドン溶液を調製し、波長365nm(i線)を含む活性エネルギー線を用いて、化合物(D)が1質量%で含まれるN-メチルピロリドン溶液の透過率を測定した場合においては、その透過率は5%以上であることが好ましい。このように化合物(D)は非常に優れた光透過性を示す。また、波長405nm(h線)を含む活性エネルギー線を用いて、化合物(D)が1質量%で含まれるN-メチルピロリドン溶液の透過率を測定した場合においては、その透過率が5%以上であることが好ましく、この場合においても非常に優れた光透過性を示す。このような化合物(D)を用いると、例えば、直接描画露光法を用いて高密度で高精細な配線形成(パターン)を有するプリント配線板を製造するに際し、波長405nm(h線)を含む活性エネルギー線を用いた場合でも、マレイミドの光ラジカル反応が効率的に起こる。波長365nm(i線)における透過率は、光硬化性により優れる樹脂組成物を得ることができることから、8%以上、10%以上、20%以上、30%以上、及び40%以上と、この順で好ましい範囲となる。波長405nm(h線)における透過率は、光硬化性により優れる樹脂組成物を得ることができることから、8%以上、10%以上、20%以上、30%以上、及び40%以上と、この順で好ましい範囲となる。なお、波長365nm(i線)における透過率、及び波長405nm(h線)における透過率において、それぞれの上限は、例えば、99.9%以下である。
カルボキシ基を1つ以上含む脂肪族化合物としては、例えば、鎖状脂肪族モノカルボン酸、脂環式モノカルボン酸、鎖状脂肪族多価カルボン酸、及び脂環式多価カルボン酸が挙げられる。これらの化合物には、分子内に、水素原子、並びにアルキル基、アルコキシ基、アリールオキシ基、アリール基、アミノアルキル基、ヒドロキシル基、アミノ基、及びカルボキシアルキル基等の置換基を有していてもよい。また、これらの化合物は、分子内に、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を有する場合には、カルボキシアルキル基とカルボキシ基が互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。
アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、tert-ブトキシ基、n-ヘキサノキシ基、及び2-メチルプロポキシ基等が挙げられる。
アリールオキシ基としては、例えば、フェノキシ基、及びp-トリルオキシ基が挙げられる。
アリール基としては、例えば、フェニル基、トルイル基、ベンジル基、メチルベンジル基、キシリル基、メシチル基、ナフチル基、及びアントリル基が挙げられる。
アミノアルキル基としては、例えば、アミノメチル基、アミノエチル基、アミノプロピル基、アミノジメチル基、アミノジエチル基、アミノジプロピル基、アミノブチル基、アミノヘキシル基、及びアミノノニル基等が挙げられる。
カルボキシアルキル基としては、例えば、カルボキシメチル基、カルボキシエチル基、カルボキシプロピル基、カルボキシブチル基、カルボキシヘキシル基、及びカルボキシノニル基等が挙げられる。
カルボキシ基を1つ以上含む芳香族化合物の母体骨格としては、例えば、安息香酸、フェニレン酢酸、サリチル酸、フタル酸、トリメリット酸、ピロメリット酸、ペンタカルボキシベンゼン、ヘキサカルボキシベンゼン、ナフタレンカルボン酸、ナフタレンジカルボン酸、ナフタレントリカルボン酸、ナフタレンテトラカルボン酸、アントラセンカルボン酸、アントラセンジカルボン酸、アントラセントリカルボン酸、アントラセンテトラカルボン酸、及びアントラセンペンタカルボン酸等が挙げられる。芳香族化合物は、これらの母体骨格の芳香環上に、例えば、水素原子、並びにアルキル基、アルコキシ基、アリールオキシ基、アリール基、アミノアルキル基、ヒドロキシル基、アミノ基、及びカルボキシアルキル基等の置換基を有していてもよい。また、これらの化合物は、分子内に、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を有する場合には、カルボキシアルキル基とカルボキシ基が互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの置換基については、前記を参照できる。
カルボキシ基を1つ以上含むヘテロ化合物の母体骨格としては、例えば、フラン、チオフェン、ピロール、イミダゾール、ピラン、ピリジン、ピリミジン、ピラジン、ピロリジン、ピペリジン、ピペラジン、モルホリン、インドール、プリン、キノリン、イソキノリン、キヌクリジン、クロメン、チアントレン、フェノチアジン、フェノキサジン、キサンテン、アクリジン、フェナジン、及びカルバゾール等のヘテロ環に、1つ以上のカルボキシ基を含む化合物が挙げられる。ヘテロ化合物は、これらの母体骨格上に、例えば、水素原子、並びにアルキル基、アルコキシ基、アリールオキシ基、アリール基、アミノアルキル基、ヒドロキシル基、アミノ基、及びカルボキシアルキル基等の置換基を有していてもよい。また、これらの化合物は、分子内に、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を有する場合には、カルボキシアルキル基とカルボキシ基が互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの置換基については、前記を参照できる。
R17は、アルカリ現像性の点から、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、又はアミノ基であることが好ましく、より優れたアルカリ現像性が得られる点から、カルボキシ基を含むことがより好ましい。
なお、安息香酸は、他のカルボキシ基を1つ以上含む化合物(D)に比べて、アルカリ現像性に劣る傾向にある。
また、kは、各々独立に、1~5の整数を示す。
また、kは、各々独立に、0~4の整数を示す。
カルボキシ基数pは、5-kの整数を示す。カルボキシ基数pは、より優れたアルカリ現像性を示す点から、1~3の整数であることが好ましい。この場合、R17の数kは、5-pの整数で2~4の整数である。
式(23)で表される化合物は、カルボキシ基を2つ以上含み、それらが互いに連結して形成された酸無水物であってもよい。
R18は、アルカリ現像性の点から、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、又はアミノ基であることが好ましく、より優れたアルカリ現像性が得られる点から、カルボキシ基を含むことがより好ましい。
また、lは、各々独立に、1~9の整数を示す。
なお、ピペリジンカルボン酸は、他のカルボキシ基を1つ以上含む化合物(B)に比べて、アルカリ現像性に劣る傾向にある。
R19は、アルカリ現像性の点から、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、又はアミノ基であることが好ましく、より優れたアルカリ現像性が得られる点から、カルボキシ基を含むことがより好ましい。
また、mは、各々独立に、1~9の整数を示す。
また、mは、各々独立に、0~8の整数を示す。
カルボキシ基数qは、9-mの整数を示す。カルボキシ基数qは、より優れたアルカリ現像性を示す点から、1~3の整数であることが好ましい。この場合、R6の数mは、9-qの整数で6~8の整数である。
式(24)で表される化合物は、カルボキシ基を2つ以上含み、それらが互いに連結して形成された酸無水物であってもよい。また、式(24)で表される化合物は、カルボキシメチル基を有する場合には、カルボキシメチル基とカルボキシ基は、それらが互いに連結して形成された酸無水物であってもよい。
R20は、アルカリ現像性の点から、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、又はアミノ基であることが好ましく、より優れたアルカリ現像性が得られる点から、カルボキシ基を含むことがより好ましい。
また、oは、各々独立に、1~5の整数を示す。
また、oは、各々独立に、0~4の整数を示す。
カルボキシ基数rは、5-oの整数を示す。カルボキシ基数rは、より優れたアルカリ現像性を示す点から、1~3の整数であることが好ましい。この場合、R7の数oは、5-rの整数で2~4の整数である。
式(25)において、カルボキシメチル基とカルボキシ基は、それらが互いに連結して形成された酸無水物であってもよい。式(25)で表される化合物は、カルボキシ基を2つ以上有する場合、それらが互いに連結して形成された酸無水物であってもよい。式(25)中、カルボキシ基数の上限は、5である。式(25)で表される化合物は、カルボキシメチル基を2つ以上有する場合、それらが互いに連結して形成された酸無水物であってもよい。式(25)中、カルボキシメチル基数の上限は、6である。
本実施形態の樹脂組成物には、本発明の効果を奏する限り、ビスマレイミド化合物(A)及びマレイミド化合物(B)以外の、マレイミド化合物(E)(成分(E)とも称す)を用いることができる。ビスマレイミド化合物(A)は、前記のとおり、光透過性に非常に優れるため、マレイミド化合物(B)と共にマレイミド化合物(E)を用いても、光硬化開始剤まで十分に光が届き、マレイミドの光ラジカル反応が効率的に起き、種々の活性エネルギー線を用いて光硬化させることができる。そのため、例えば、波長365nmを含む活性エネルギー線、又は405nmを含む活性エネルギー線を用いても、光が光硬化開始剤まで十分に届き、光硬化開始剤から発生したラジカルを用いたラジカル反応が進行し、マレイミド化合物(E)が配合されている組成物においても光硬化が可能となる。マレイミド化合物(E)としては、ビスマレイミド化合物(A)及びマレイミド化合物(B)との相溶性がより良好であり、そのうえで、ワニスに用いた場合に、ワニス中において液状成分が少なくなるマレイミド化合物を用いることが好ましい。
本実施形態の樹脂組成物には、塗膜性や耐熱性等の諸特性を向上させるために、充填材(F)(成分(F)とも称す)を用いることができる。充填材(F)としては、絶縁性を有し、光硬化に用いる種々の活性エネルギー線に対する透過性を阻害しないものであることが好ましく、波長365nm(i線)、及び/又は波長405nm(h線)を活性エネルギー線に対する透過性を阻害しないものであることがより好ましい。
これらの充填材(F)は、後述のシランカップリング剤等で表面処理されていてもよい。
本実施形態の樹脂組成物には、充填材の分散性、ポリマー及び/又は樹脂と、充填材との接着強度を向上させるために、シランカップリング剤及び/又は湿潤分散剤を併用することできる。
これらのシランカップリング剤としては、一般に無機物の表面処理に使用されているシランカップリング剤であれば、特に限定されない。例えば、3-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、3-アミノプロピルジメトキシメチルシラン、3-アミノプロピルジエトキシメチルシラン、N-β-(アミノエチル)-γ-アミノプロピルトリメトキシラン、N-(2-アミノエチル)-3-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルジメトキシメチルシラン、N-(2-アミノエチル)-3-アミノプロピルジエトキシメチルシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、[3-(6-アミノヘキシルアミノ)プロピル]トリメトキシシラン、及び[3-(N,N-ジメチルアミノ)-プロピル]トリメトキシシランなどのアミノシラン系;γ-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルジメトキシメチルシラン、3-グリシドキシプロピルジエトキシメチルシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、及び[8-(グリシジルオキシ)-n-オクチル]トリメトキシシランなどのエポキシシラン系;ビニルトリス(2-メトキシエトキシ)シラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ジメトキシメチルビニルシラン、ジエトキシメチルビニルシラン、トリメトキシ(7-オクテン-1-イル)シラン、及びトリメトキシ(4-ビニルフェニル)シランなどのビニルシラン系;3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルジメトキシメチルシラン、3-メタクリロキシプロピルジエトキシメチルシランなどのメタクリルシラン系;3-アクリロキシプロピルトリメトキシシラン、及び3-アクリロキシプロピルトリエトキシシランなどのアクリルシラン系;3-イソシアネートプロピルトリメトキシシラン、及び3-イソシアネートプロピルトリエトキシシランなどのイソシアネートシラン系;トリス-(トリメトキシシリルプロピル)イソシアヌレートなどのイソシアヌレートシラン系;3-メルカプトプロピルトリメトキシシラン、及び3-メルカプトプロピルジメトキシメチルシランなどのメルカプトシラン系;3-ウレイドプロピルトリエトキシシランなどのウレイドシラン系;p-スチリルトリメトキシシランなどのスチリルシラン系;N-β-(N-ビニルベンジルアミノエチル-γ-アミノプロピルトリメトキシシラン塩酸塩などのカチオニックシラン系;[3-(トリメトキシシリル)プロピル]コハク酸無水物などの酸無水物系;フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジメトキシメチルフェニルシラン、ジエトキシメチルフェニルシラン、及びp-トリルトリメトキシシランなどのフェニルシラン系;トリメトキシ(1-ナフチル)シランなどのアリールシラン系が挙げられる。これらのシランカップリング剤は、1種単独又は2種以上を適宜混合して使用することも可能である。
樹脂組成物において、湿潤分散剤の含有量は、通常、ビスマレイミド化合物(A)及びマレイミド化合物(B)の合計100質量部に対して、0.1~10質量部である。
本実施形態では、本発明の効果を奏する限り、硬化した硬化物の難燃性、耐熱性、及び熱膨張特性等の特性に応じて、ビスマレイミド化合物(A)、マレイミド化合物(B)、光硬化開始剤(C)、カルボキシ基を1つ以上含む化合物(D)、及びマレイミド化合物(E)以外の、シアン酸エステル化合物、フェノール樹脂、オキセタン樹脂、ベンゾオキサジン化合物、エポキシ樹脂、及びその他の化合物等、様々な種類の化合物及び樹脂を用いることができる。また、これらの化合物及び樹脂は、波長365nm(i線)を含む活性エネルギー線、及び/又は405nm(h線)を含む活性エネルギー線で露光した場合に、樹脂組成物が感光して、光硬化することが好ましい。
これらの化合物及び樹脂は、1種単独又は2種以上を適宜混合して使用することも可能である。
シアン酸エステル化合物としては、シアナト基(シアン酸エステル基)が少なくとも1個置換された芳香族部分を分子内に有する樹脂であれば特に限定されない。
また、式(26)におけるアルキル基及びRaにおけるアリール基中の水素原子は、フッ素原子、及び塩素原子等のハロゲン原子、メトキシ基、及びフェノキシ基等のアルコキシル基、又はシアノ基等で置換されていてもよい。
アルケニル基の具体例としては、ビニル基、(メタ)アリル基、イソプロペニル基、1-プロペニル基、2-ブテニル基、3-ブテニル基、1,3-ブタンジエニル基、2-メチル-2-プロペニル、2-ペンテニル基、及び2-ヘキセニル基等が挙げられる。
アリール基の具体例としては、フェニル基、キシリル基、メシチル基、ナフチル基、フェノキシフェニル基、エチルフェニル基、o-,m-又はp-フルオロフェニル基、ジクロロフェニル基、ジシアノフェニル基、トリフルオロフェニル基、メトキシフェニル基、及びo-,m-又はp-トリル基等が挙げられる。
アルコキシル基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、及びtert-ブトキシ基等が挙げられる。
式(26)のXにおける窒素数1~10の2価の有機基としては、イミノ基、及びポリイミド基等が挙げられる。
式(27)のAr2及び式(28)のAr3の具体例としては、式(27)に示す2個の炭素原子、又は式(28)に示す2個の酸素原子が、1,4位又は1,3位に結合するベンゼンジイル基、2個の炭素原子又は2個の酸素原子が4,4'位、2,4'位、2,2'位、2,3'位、3,3'位、又は3,4'位に結合するビフェニルジイル基、及び、2個の炭素原子又は2個の酸素原子が、2,6位、1,5位、1,6位、1,8位、1,3位、1,4位、又は2,7位に結合するナフタレンジイル基が挙げられる。
式(27)のRb、Rc、Rd、Re、Rf、及びRg、並びに式(28)のRi、及びRjにおけるアルキル基及びアリール基は、式(26)におけるものと同義である。
フェノール樹脂としては、1分子中に2個以上のヒドロキシル基を有するフェノール樹脂であれば、一般に公知のものを使用できる。例えば、ビスフェノールA型フェノール樹脂、ビスフェノールE型フェノール樹脂、ビスフェノールF型フェノール樹脂、ビスフェノールS型フェノール樹脂、フェノールノボラック樹脂、ビスフェノールAノボラック型フェノール樹脂、グリシジルエステル型フェノール樹脂、アラルキルノボラック型フェノール樹脂、ビフェニルアラルキル型フェノール樹脂、クレゾールノボラック型フェノール樹脂、多官能フェノール樹脂、ナフトール樹脂、ナフトールノボラック樹脂、多官能ナフトール樹脂、アントラセン型フェノール樹脂、ナフタレン骨格変性ノボラック型フェノール樹脂、フェノールアラルキル型フェノール樹脂、ナフトールアラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、ビフェニル型フェノール樹脂、脂環式フェノール樹脂、ポリオール型フェノール樹脂、リン含有フェノール樹脂、重合性不飽和炭化水素基含有フェノール樹脂、及び水酸基含有シリコーン樹脂類等が挙げられる。これらのフェノール樹脂は、1種単独又は2種以上を適宜混合して使用することも可能である。
オキセタン樹脂としては、一般に公知のものを使用できる。例えば、オキセタン、2-メチルオキセタン、2,2-ジメチルオキセタン、3-メチルオキセタン、3,3-ジメチルオキセタン等のアルキルオキセタン、3-メチル-3-メトキシメチルオキセタン、3,3-ジ(トリフルオロメチル)パーフルオキセタン、2-クロロメチルオキセタン、3,3-ビス(クロロメチル)オキセタン、ビフェニル型オキセタン、OXT-101(東亞合成(株)製、商品名)、OXT-121(東亞合成(株)製、商品名)、及びOXT-221(東亞合成(株)製、商品名)等が挙げられる。これらのオキセタン樹脂は、1種単独又は2種以上を適宜混合して使用することも可能である。
ベンゾオキサジン化合物としては、1分子中に2個以上のジヒドロベンゾオキサジン環を有する化合物であれば、一般に公知のものを用いることができる。例えば、ビスフェノールA型ベンゾオキサジンBA-BXZ(小西化学工業(株)製、商品名)ビスフェノールF型ベンゾオキサジンBF-BXZ(小西化学工業(株)製、商品名)、ビスフェノールS型ベンゾオキサジンBS-BXZ(小西化学工業(株)製、商品名)、及びフェノールフタレイン型ベンゾオキサジン等が挙げられる。これらのベンゾオキサジン化合物は、1種単独又は2種以上を適宜混合して使用することも可能である。
エポキシ樹脂としては、特に限定されず、一般に公知のものを使用できる。例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールE型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、キシレンノボラック型エポキシ樹脂、多官能フェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフタレン骨格変性ノボラック型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、アントラセン型エポキシ樹脂、3官能フェノール型エポキシ樹脂、4官能フェノール型エポキシ樹脂、トリグリシジルイソシアヌレート、グリシジルエステル型エポキシ樹脂、脂環式エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、フェノールアラルキルノボラック型エポキシ樹脂、ナフトールアラルキルノボラック型エポキシ樹脂、アラルキルノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ポリオール型エポキシ樹脂、リン含有エポキシ樹脂、グリシジルアミン、ブタジエン等の二重結合をエポキシ化した化合物、水酸基含有シリコーン樹脂類とエピクロルヒドリンとの反応により得られる化合物、及びこれらのハロゲン化物が挙げられる。これらのエポキシ樹脂は、1種単独又は2種以上を適宜混合して使用することも可能である。
その他の化合物としては、エチルビニルエーテル、プロピルビニルエーテル、ヒドロキシエチルビニルエーテル、及びエチレングリコールジビニルエーテル等のビニルエーテル類;スチレン、メチルスチレン、エチルスチレン、及びジビニルベンゼン等のスチレン類;トリアリルイソシアヌレート、トリメタアリルイソシアヌレート、及びビスアリルナジイミド等が挙げられる。これらの化合物は、1種単独又は2種以上を適宜混合して使用することも可能である。
樹脂組成物において、その他の化合物の含有量は、通常、ビスマレイミド化合物(A)及びマレイミド化合物(B)の合計100質量部に対して、0.01~40質量部である。
本実施形態の樹脂組成物には、必要に応じて、有機溶剤を含有していてもよい。有機溶剤を用いると、樹脂組成物の調製時における粘度を調整することができる。有機溶剤の種類は、樹脂組成物中の樹脂の一部又は全部を溶解可能なものであれば、特に限定されない。
このような有機溶剤としては、例えば、ジクロロメタン、クロロホルム、ジクロロエタン、及びクロロベンゼン等のハロゲン溶媒;ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、テトラヒドロフラン、ジオキサン、及びアセトニトリル等の非プロトン性極性溶媒;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、及びシクロヘキサノン等のケトン溶媒;2-エトキシエタノール、及びプロピレングリコールモノメチルエーテル等のセロソルブ溶媒;メタノール、エタノール、プロパノール、イソプロパノール、及びブタノール等の脂肪族アルコール溶媒;フェノール、及びクレゾール等の芳香族基含有フェノール溶媒;乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソアミル、メトキシプロピオン酸メチル、ヒドロキシイソ酪酸メチル、γ-ブチロラクトン、及びプロピレングリコールモノメチルエーテルアセテート等のエステル溶媒;トルエン、及びキシレン等の芳香族炭化水素溶媒等が挙げられる。
本実施形態の樹脂組成物には、本実施形態の特性が損なわれない範囲において、これまでに挙げられていない熱硬化性樹脂、熱可塑性樹脂、及びそのオリゴマー、並びにエラストマー類等の種々の高分子化合物;これまでに挙げられていない難燃性の化合物;添加剤等の併用も可能である。これらは一般に使用されているものであれば、特に限定されない。例えば、難燃性の化合物では、メラミンやベンゾグアナミン等の窒素含有化合物;オキサジン環含有化合物;リン系化合物のホスフェート化合物、芳香族縮合リン酸エステル、及び含ハロゲン縮合リン酸エステル等のリン系化合物が挙げられる。添加剤としては、紫外線吸収剤、酸化防止剤、蛍光増白剤、光増感剤、染料、顔料、増粘剤、滑剤、消泡剤、表面調整剤、光沢剤、重合禁止剤、及び熱硬化促進剤等が挙げられる。これらの成分は、1種単独又は2種以上を適宜混合して使用することも可能である。
樹脂組成物において、その他の成分の含有量は、通常、ビスマレイミド化合物(A)及びマレイミド化合物(B)の合計100質量部に対して、それぞれ0.1~10質量部である。
本実施形態の樹脂組成物は、ビスマレイミド化合物(A)、マレイミド化合物(B)、必要に応じて、光硬化開始剤(C)、カルボキシ基を1つ以上含む化合物(D)、マレイミド化合物(E)、充填材(F)、及びその他の樹脂、その他の化合物、並びに添加剤等を適宜混合することにより調製することができる。樹脂組成物の製造方法は、例えば、前記した各成分を順次溶剤に配合し、十分に攪拌する方法が挙げられる。本実施形態の樹脂組成物は、少なくとも、ビスマレイミド化合物(A)と、マレイミド化合物(B)とを含み、有機溶媒に対して良好な溶解性を有する。また、光重合開始剤とカルボキシル基を1つ以上含む化合物とを更に含むことで、優れた光硬化性と、優れたアルカリ現像性をも有する。そして、樹脂組成物から得られるワニスは、適度な粘度を有し、液状成分が少ないので、ワニスを乾燥して得られる樹脂シートは、良好な光硬化性及びアルカリ現像性を有しながら、タック性が良好に抑制される。なお、ワニスの調製に使用する有機溶媒は、特に限定されず、その具体例は、前記したとおりである。
本実施形態の樹脂組成物は、絶縁性の樹脂組成物が必要とされる用途に使用することができ、特に限定されない。例えば、感光性フィルム、支持体付き感光性フィルム、プリプレグ、樹脂シート、回路基板(積層板用途、多層プリント配線板用途等)、ソルダーレジスト、アンダーフィル材、ダイボンディング材、半導体封止材、穴埋め樹脂、及び部品埋め込み樹脂等に使用することができる。それらの中でも、樹脂組成物は、溶解性、光硬化性及びアルカリ現像性に優れ、また、樹脂シート及びプリント配線板に用いた際に、タック性が好適に抑制されることから、多層プリント配線板の絶縁層用として、又はソルダーレジスト用として好適に使用することができる。
硬化物は、樹脂組成物を硬化させて得られる。硬化物は、例えば、樹脂組成物を溶融又は溶媒に溶解させた後、型内に流し込み、光を用いて通常の条件で硬化させることにより得ることができる。光の波長領域は、光重合開始剤等により効率的に硬化が進む100~500nmの範囲で硬化させることが好ましい。
本実施形態の樹脂シートは、支持体と、支持体の片面又は両面に配された樹脂層と、を有し、樹脂層が、本実施形態の樹脂組成物を含む、支持体付き樹脂シートである。樹脂シートは、樹脂組成物を支持体上に塗布、及び乾燥して製造することができる。樹脂シートにおける樹脂層は、タック性が良好に抑制されており、優れた光硬化性及びアルカリ現像性を有する。
樹脂層側を保護フィルムで保護することにより、樹脂層表面へのゴミ等の付着やキズを防止することができる。また、樹脂層は、光硬化性及びアルカリ現像性を有しながら、タック性が良好に抑制されているため、樹脂層を硬化した後において、保護フィルムを容易に剥離することができる。保護フィルムとしては、樹脂フィルムと同様の材料により構成されたフィルムを用いることができる。保護フィルムの厚さは、1~50μmの範囲であることが好ましく、5~40μmの範囲であることがより好ましい。厚さが1μm未満では、保護フィルムの取り扱い性が低下する傾向にあり、50μmを超えると廉価性に劣る傾向にある。なお、保護フィルムは、樹脂層と支持体との接着力に対して、樹脂層と保護フィルムとの接着力の方が小さいものが好ましい。
塗布方法は、例えば、ロールコーター、コンマコーター、グラビアコーター、ダイコーター、バーコーター、リップコーター、ナイフコーター、及びスクイズコーター等を用いた公知の方法で行うことができる。乾燥は、例えば、60~200℃の乾燥機中で、1~60分加熱させる方法等により行うことができる。
本実施形態の多層プリント配線板は、絶縁層と、絶縁層の片面又は両面に形成された導体層とを有し、絶縁層が、本実施形態の樹脂組成物を含む。絶縁層は、例えば、樹脂シートを1枚以上重ねて硬化して得ることもできる。絶縁層と導体層のそれぞれの積層数は、目的とする用途に応じて適宜積層数を設定することができる。また、絶縁層と導体層の順番も特に限定されない。導体層としては、各種プリント配線板材料に用いられる金属箔であってもよく、例えば、銅、及びアルミニウム等の金属箔が挙げられる。銅の金属箔としては、圧延銅箔、及び電解銅箔等の銅箔が挙げられる。導体層の厚みは、通常、1~100μmである。具体的には、以下の方法により製造することができる。
ラミネート工程では、樹脂シートの樹脂層側を、真空ラミネーターを用いて回路基板の片面又は両面にラミネートする。回路基板としては、例えば、ガラスエポキシ基板、金属基板、セラミック基板、シリコン基板、半導体封止樹脂基板、ポリエステル基板、ポリイミド基板、BTレジン基板、及び熱硬化型ポリフェニレンエーテル基板等が挙げられる。なお、回路基板とは、前記のような基板の片面又は両面にパターン加工された導体層(回路)が形成された基板をいう。また、導体層と絶縁層とを交互に積層してなる多層プリント配線板において、多層プリント配線板の最外層の片面又は両面がパターン加工された導体層(回路)となっている基板も回路基板に含まれる。なお、多層プリント配線板に積層されている絶縁層は、本実施形態の樹脂シートを1枚以上重ねて硬化して得られた絶縁層であってもよく、本実施形態の樹脂シートと、本実施形態の樹脂シートと異なる公知の樹脂シートとをそれぞれ1枚以上重ねて得られた絶縁層であってもよい。なお、本実施形態の樹脂シートと、本実施形態の樹脂シートと異なる公知の樹脂シートとの重ね方は、特に限定されない。導体層表面には、黒化処理、及び/又は銅エッチング等により予め粗化処理が施されていてもよい。ラミネート工程において、樹脂シートが保護フィルムを有している場合には、保護フィルムを剥離除去した後、必要に応じて樹脂シート及び回路基板をプレヒートし、樹脂シートの樹脂層を加圧及び加熱しながら回路基板に圧着する。本実施形態においては、真空ラミネート法により減圧下で回路基板に樹脂シートの樹脂層をラミネートする方法が好適に用いられる。
露光工程では、ラミネート工程により、回路基板上に樹脂層が設けられた後、樹脂層の所定部分に光源として、活性エネルギー線を照射し、照射部の樹脂層を硬化させる。得られる樹脂層は、タック性が好適に抑制される。なお、化合物(D)は、露光工程において、光硬化反応を阻害しない。
照射は、マスクパターンを通してもよいし、直接照射する直接描画法を用いてもよい。活性エネルギー線としては、例えば、紫外線、可視光線、電子線、及びX線等が挙げられる。活性エネルギー線の波長としては、例えば、200~600nmの範囲である。紫外線を用いる場合、その照射量はおおむね10~1000mJ/cm2である。また、ステッパー露光法を用いて高密度で高精細な配線形成(パターン)を有するプリント配線板を製造するに際しては、活性エネルギー線として、例えば、波長365nm(i線)を含む活性エネルギー線を用いることが好ましい。波長365nm(i線)を含む活性エネルギー線を用いた場合、その照射量は、おおむね10~10,000mJ/cm2である。直接描画露光法を用いて高密度で高精細な配線形成(パターン)を有するプリント配線板を製造するに際しては、活性エネルギー線として、例えば、波長405nm(h線)を含む活性エネルギー線を用いることが好ましい。波長405nm(h線)を含む活性エネルギー線を用いた場合、その照射量は、おおむね10~10,000mJ/cm2である。
マスクパターンを通す露光方法には、マスクパターンを多層プリント配線板に密着させて行う接触露光法と、密着させずに平行光線を使用して露光する非接触露光法とがあるが、どちらを用いてもかまわない。また、樹脂層上に支持体が存在している場合は、支持体上から露光してもよいし、支持体を剥離後に露光してもよい。
樹脂層上に支持体が存在していない場合には、露光工程後、直接アルカリ現像にて光硬化されていない部分(未露光部)を除去し、現像することにより、絶縁層のパターンを形成することができる。
また、樹脂層上に支持体が存在している場合には、露光工程後、その支持体を除去した後に、アルカリ現像にて光硬化されていない部分(未露光部)を除去し、現像することにより、絶縁層のパターンを形成することができる。
本実施形態の樹脂組成物を含む未露光の樹脂層は、優れたアルカリ現像性を有するため、高精細なパターンを有するプリント配線板を得ることができる。
本実施形態では、アルカリ現像工程終了後、ポストベーク工程を行い、絶縁層(硬化物)を形成する。ポストベーク工程としては、高圧水銀ランプによる紫外線照射工程やクリーンオーブンを用いた加熱工程等が挙げられ、これらを併用することも可能である。紫外線を照射する場合は、必要に応じてその照射量を調整することができ、例えば、0.05~10J/cm2程度の照射量で照射を行うことができる。また加熱の条件は、必要に応じて適宜選択できるが、好ましくは150~220℃で20~180分間の範囲、より好ましくは160~200℃で30~150分間の範囲で選択される。
絶縁層(硬化物)を形成後、乾式めっきにより絶縁層表面に導体層を形成する。
なお、導体層の形成に際して、乾式めっき前に、絶縁層表面に対して、表面改質処理を行ってもよい。表面改質処理としては、プラズマエッチング処理、逆スパッタ処理、及びコロナ処理等の公知の方法を使用することができる。
乾式めっきとしては、蒸着法、スパッタリング法、及びイオンプレーティング法等の公知の方法を使用することができる。蒸着法(真空蒸着法)は、例えば、多層プリント配線板を真空容器内に入れ、金属を加熱蒸発させることにより、絶縁層上に金属膜を形成することができる。スパッタリング法も、例えば、多層プリント配線板を真空容器内に入れ、アルゴン等の不活性ガスを導入し、直流電圧を印加して、イオン化した不活性ガスをターゲット金属に衝突させ、叩き出された金属により絶縁層上に金属膜を形成することができる。
本実施形態の半導体装置は、本実施形態の樹脂組成物を含む。具体的には、以下の方法により製造することができる。多層プリント配線板の導通箇所に、半導体チップを実装することにより半導体装置を製造することができる。ここで、導通箇所とは、多層プリント配線板における電気信号を伝える箇所のことであって、その場所は表面であっても、埋め込まれた箇所であってもよい。また、半導体チップは、半導体を材料とする電気回路素子であれば特に限定されない。
〔透過率、及び吸光度〕
ビスマレイミド化合物(A)として、日本化薬(株)製MIZ-001(商品名、質量平均分子量(Mw):3000)を用いて、このMIZ-001(商品名)が1質量%で含まれるクロロホルム溶液を調製し、UV-vis測定装置((株)日立ハイテクノロジーズ製日立分光光度計 U-4100(商品名))を用いて、波長365nm、及び405nmにおけるそれぞれの透過率の測定を行った。
同様に、光硬化開始剤として、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1(IGM Resins B.V.社製Omnirad(登録商標)369(商品名))、及び2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン(IGM Resins社製Omnirad B.V.(登録商標)907(商品名))を用いて、波長365nm、及び405nmにおけるそれぞれの吸光度の測定を行った。
結果を表1に示す。
次のようにして、式(19)で表される化合物(TMDM)を合成した。
〔アミド酸化合物(以下、MA-TMDAと略記する。)の合成〕
まず、式(31)で表されるMA-TMDAを下記の方法にて合成した。
反応溶液を一部分取し、水と、酢酸エチルとを加えて振盪した。その後、有機層を取り出して、硫酸マグネシウムで乾燥した。上澄みを40℃で溶媒留去し、黄色オイルを得た。1H-NMR測定を行い、式(31)で表されるMA-TMDAであることを確認した。
式(31)で表されるMA-TMDAの1H-NMRの帰属を以下に示す。また、1H-NMRチャートを図1に示す。
前記の反応溶液に、p-トルエンスルホン酸一水和物0.67g(3.5mmol)を加え、127℃で2.5時間加熱還流した。室温(25℃)まで冷却した後、冷却後の反応溶液を、飽和炭酸水素ナトリウム水溶液50mLと、酢酸エチル100mLとの混合溶液に攪拌しながら注いだ。更に、水100mLと、酢酸エチル100mLとを加えて撹拌し、5分間静置した。その後、分液し、水層を酢酸エチル50mLで3回抽出した。有機層を全て合わせて、水100mLで1回、飽和食塩水10mLで1回、飽和食塩水5mLで2回洗浄した。硫酸マグネシウムで乾燥して、固体分を濾別した後、40℃で溶媒留去し、黄色固体を得た。
得られた黄色固体をアセトン6.5mLに溶解させ、アセトン溶液を水300mLに注いだ。析出した固体をろ取し、少量のイソプロピルアルコール(IPA)で洗浄した後、50℃で20時間減圧乾燥して黄色固体5.71質量部を得た。1H-NMR測定を行い、式(19)で表されるマレイミド化合物(TMDM)であること確認した。
TMDMの1H-NMRの帰属を以下に示す。また、1H-NMRチャートを図2に示す。
(樹脂組成物及び樹脂シートの作成)
ビスマレイミド化合物(A)として、MIZ-001(商品名)を60質量部と、マレイミド化合物(B)として、群栄化学工業(株)社製BCPH13(商品名)を25質量部と、マレイミド化合物(B)として、TMDMを15質量部と、光硬化開始剤(C)として、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(Omnirad(登録商標)819(商品名)を5質量部と、カルボキシ基を1つ以上含む化合物(D)として、シス-4-シクロヘキセン-1,2-ジカルボン酸無水物(東京化成工業(株)製)を10質量部に対して、有機溶剤として、メチルエチルケトン(出光興産(株)製)168.8質量部を混合し、90℃湯浴で攪拌してワニス(樹脂組成物)を得た。このワニスを厚さ38μmのPETフィルム(ユニチカ(株)製ユニピール(登録商標)TR1-38(商品名))上に滴下し、スピンコート(300rpmで10秒間、その後1000rpmで30秒間)により塗膜を形成した。得られた塗膜を90℃で5分間乾燥して、PETフィルムを支持体とし樹脂層の厚さが10μmである樹脂シートを得た。
得られた樹脂シートの樹脂面を張り合わせ、真空ラミネーター(ニッコー・マテリアルズ(株)製)を用いて、30秒間真空引き(5.0hPa以下)を行った後、圧力10kgf/cm2、温度70℃で30秒間の積層成形を行った。さらに圧力7kgf/cm2、温度70℃で60秒間の積層成形を行うことで、両面に支持体を有する評価用樹脂を得た。
内層回路を形成したガラス布基材BT(ビスマレイミド・トリアジン)樹脂両面銅張積層板(銅箔厚さ18μm、厚み0.2mm、三菱ガス化学(株)製CCL(登録商標)-HL832NS(商品名))の両面をメック(株)製CZ8100(商品名)にて銅表面の粗化処理を行い、内層回路基板を得た。
得られた樹脂シートの樹脂面を、前記内層回路基板上の銅表面(片面)に配置し、真空ラミネーター(ニッコー・マテリアルズ(株)製)を用いて、30秒間真空引き(5.0hPa以下)を行った後、圧力10kgf/cm2、温度70℃で30秒間の積層成形を行った。さらに圧力10kgf/cm2、温度70℃で60秒間の積層成形を行うことで内層回路基板と樹脂層と支持体が積層された評価用積層体を得た。
ビスマレイミド化合物(A)として、MIZ-001(商品名)60質量部の代わりに、MIZ-001(商品名)50質量部を用い、マレイミド化合物(B)として、TMDM15質量部の代わりに、TMDM25質量部を用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
ビスマレイミド化合物(A)として、MIZ-001(商品名)60質量部の代わりに、MIZ-001(商品名)55質量部を用い、マレイミド化合物(B)として、TMDM15質量部の代わりに、TMDM20質量部を用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
ビスマレイミド化合物(A)として、MIZ-001(商品名)60質量部の代わりに、MIZ-001(商品名)65質量部を用い、マレイミド化合物(B)として、TMDM15質量部の代わりに、TMDM10質量部を用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物(B)として、TMDM15質量部の代わりに、式(20)で表されるケイ・アイ化成(株)製BMI-70(商品名)15質量部を用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物(B)として、TMDM15質量部の代わりに、式(21)で表されるケイ・アイ化成(株)製BMI-80(商品名)15質量部を用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物(B)として、TMDM15質量部の代わりに、式(22)で表される大和化成工業(株)製BMI-2300(商品名)15質量部を用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物(B)として、群栄化学工業(株)社製BCPH13(商品名)25質量部の代わりに、式(18)で表される日本化薬(株)社製MIR-3000(商品名)25質量部を用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物(B)として、TMDM15質量部の代わりに、式(20)で表されるケイ・アイ化成(株)製BMI-70(商品名)15質量部を用いた以外は、実施例8と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物(B)として、TMDM15質量部の代わりに、式(21)で表されるケイ・アイ化成(株)製BMI-80(商品名)15質量部を用いた以外は、実施例8と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物(B)として、TMDM15質量部の代わりに、式(22)で表される大和化成工業(株)製BMI-2300(商品名)15質量部を用いた以外は、実施例8と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
光硬化開始剤(C)として、Omnirad(登録商標)819(商品名)を5質量部の代わりに、Omnirad(登録商標)369(商品名)を5質量部用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
光硬化開始剤(C)として、Omnirad(登録商標)819(商品名)を5質量部の代わりに、Omnirad(登録商標)907(商品名)を5質量部用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
ビスマレイミド化合物として、MIZ-001(商品名)を60質量部と、光硬化開始剤として、Omnirad(登録商標)819(商品名)を5質量部と、カルボキシ基を1つ以上含む化合物として、シス-4-シクロヘキセン-1,2-ジカルボン酸無水物(東京化成工業(株)製)を10質量部に対して、有機溶剤として、メチルエチルケトン112.5質量部を混合し、90℃湯浴で攪拌してワニス(樹脂組成物)を得た。このワニスを用いて、実施例1と同様にして、樹脂シートを得た。また、この樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
ビスマレイミド化合物として、MIZ-001(商品名)を60質量部と、マレイミド化合物として、群栄化学工業(株)社製BCPH13(商品名)を25質量部と、光硬化開始剤として、Omnirad(登録商標)819(商品名)を5質量部と、カルボキシ基を1つ以上含む化合物として、シス-4-シクロヘキセン-1,2-ジカルボン酸無水物(東京化成工業(株)製)を10質量部に対して、有機溶剤として、メチルエチルケトン150質量部を混合し、90℃湯浴で攪拌してワニス(樹脂組成物)を得た。このワニスを用いて、実施例1と同様にして、樹脂シートを得た。また、この樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物として、群栄化学工業(株)社製BCPH13(商品名)を25質量部の代わりに、TMDMを15質量部用いた以外は、比較例2と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
ビスマレイミド化合物として、MIZ-001(商品名)60質量部の代わりに、MIZ-001(商品名)50質量部を用い、マレイミド化合物として、TMDMを15質量部の代わりに、式(32)で表される川口化学工業(株)社製IPBM(商品名)を25質量部用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
ビスマレイミド化合物として、MIZ-001(商品名)60質量部の代わりに、MIZ-001(商品名)50質量部を用い、マレイミド化合物として、TMDMを15質量部の代わりに、式(33)で表される大和化成工業(株)製BMI-TMH(商品名)を25質量部用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
ビスマレイミド化合物として、MIZ-001(商品名)60質量部の代わりに、MIZ-001(商品名)50質量部を用い、マレイミド化合物として、TMDMを15質量部の代わりに、式(34)で表されるDesigner Molecules Inc.(株)製BMI-6100(商品名、式(34)中、xは18、及びyは18である)を25質量部用いた以外は、実施例1と同様にして、ワニス及び樹脂シート得た。また、樹脂シートを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
実施例及び比較例で得られた、ワニス(樹脂組成物)、評価用樹脂、及び樹脂シートを、以下の方法により測定し、評価した。それらの結果を表2、3及び図3に示す。
得られたワニス(樹脂組成物)中において、樹脂成分の溶け残りを目視にて観察した。溶解性は、以下の基準に従って目視にて評価した。
「AA」:ワニス中において、溶け残りが全く観察されなかったものを「AA」とした。
「CC」:ワニス中において、溶け残りがわずかでも観察されたものを「CC」とした。
波長200~600nmを含む活性エネルギー線を照射可能な光源(ユーヴィックス(株)製Omnicure(登録商標)S2000(商品名))を付属したフォトDSC(ティー・エイ・インスツルメント・ジャパン(株)製DSC-2500(商標名))を用い、得られた評価用樹脂に、波長200~600nmを含む活性エネルギー線を、照度30mW、露光時間3.5分間照射して、横軸が時間(sec)、縦軸がヒートフロー(mW)のグラフを得た。
また、光源として、波長405nm(h線)フィルターを用いて、波長405nm(h線)を含む活性エネルギー線を用いたこと以外は、前記と同様の条件により、横軸が時間(sec)、縦軸がヒートフロー(mW)のグラフを得た。
それぞれのグラフにおいて、グラフの終点から、水平に線を引いた際のピーク面積をエンタルピー(J/g)とした。硬化性は、以下の基準に従って評価した。
「AA」:エンタルピーが1(J/g)以上であった。
「CC」:エンタルピーが1(J/g)未満であった。
なお、エンタルピーが1(J/g)以上とは、所定の波長における露光により、樹脂の硬化が十分に進行することを意味した。
得られた樹脂シートにおいて、樹脂面に指を押し当て1秒間保持した後、指を持ち上げた際に支持体が持ち上がる高さによって、以下の基準でタック性を評価した。
「AA」:支持体が持ち上がる高さが基準面から1cm未満であった。
「CC」:支持体が持ち上がる高さが基準面から1cm以上であった。
得られた評価用積層体に、波長405nm(h線)を含む活性エネルギー線を照射可能な光源(ミカサ(株)製MA-20(商品名))を用いて、支持体の上から、照射量200mJ/cm2にて照射し、樹脂層の半分を露光し、残りを未露光とした。その後、支持体(PETフィルム)を剥離し、2.38%TMAH(水酸化テトラメチルアンモニウム)水溶液(現像液、(株)トクヤマ社製)中で90秒間振とうした。その際、60秒間振とう時に現像性を確認し、溶け残りがある場合はさらに30秒間、振とうを行った。アルカリ現像性は、以下の基準に従って目視にて評価した。
「AA」:露光部は不溶であるが、未露光部は60秒間の振とうで溶解する。
「CC」:露光部及び未露光部共に不溶である。
また、実施例1及び比較例6で得られたそれぞれの樹脂シートを用いて行ったアルカリ現像後の写真を図3に示した。
Claims (9)
- 下記式(1)で表される構成単位と、分子鎖の両末端にマレイミド基と、を含む、ビスマレイミド化合物(A)と、
下記式(2)で表される化合物、下記式(3)で表される化合物、下記式(4)で表される化合物、下記式(5)で表される化合物、下記式(6)で表される化合物、及び下記式(7)で表される化合物からなる群より選択される少なくとも2種のマレイミド化合物(B)と、を含む、樹脂組成物。
- 光硬化開始剤(C)を更に含む、請求項1に記載の樹脂組成物。
- カルボキシ基を1つ以上含む化合物(D)を更に含む、請求項1~3のいずれか一項に記載の樹脂組成物。
- 前記カルボキシ基を1つ以上含む化合物(D)が、下記式(10)で表される化合物、下記式(11)で表される化合物、下記式(12)で表される化合物、及び下記式(13)で表される化合物からなる群より選択される少なくとも1種である、請求項4に記載の樹脂組成物。
- 支持体と、
前記支持体の片面又は両面に配された樹脂層と、を有し、
前記樹脂層が、請求項1~5のいずれか一項に記載の樹脂組成物を含む、
樹脂シート。 - 前記樹脂層の厚さが1~50μmである、請求項6に記載の樹脂シート。
- 絶縁層と、
前記絶縁層の片面又は両面に形成された導体層と、
を有し、
前記導体層が、請求項1~5のいずれか一項に記載の樹脂組成物を含む、多層プリント配線板。 - 請求項1~5のいずれか一項に記載の樹脂組成物を含む、半導体装置。
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WO2022264984A1 (ja) * | 2021-06-15 | 2022-12-22 | 三菱瓦斯化学株式会社 | 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 |
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EP4074740A4 (en) | 2023-01-11 |
US20230066153A1 (en) | 2023-03-02 |
TW202134348A (zh) | 2021-09-16 |
TWI832024B (zh) | 2024-02-11 |
CN114787276A (zh) | 2022-07-22 |
JP7014339B2 (ja) | 2022-02-01 |
JPWO2021117762A1 (ja) | 2021-12-09 |
US11643493B2 (en) | 2023-05-09 |
CN114787276B (zh) | 2023-03-21 |
KR20220048486A (ko) | 2022-04-19 |
KR102479615B1 (ko) | 2022-12-20 |
EP4074740A1 (en) | 2022-10-19 |
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