WO2020175537A1 - Resin composition, prepreg, metal foil-clad laminate board, resin composite sheet, and, printed circuit board - Google Patents
Resin composition, prepreg, metal foil-clad laminate board, resin composite sheet, and, printed circuit board Download PDFInfo
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- WO2020175537A1 WO2020175537A1 PCT/JP2020/007686 JP2020007686W WO2020175537A1 WO 2020175537 A1 WO2020175537 A1 WO 2020175537A1 JP 2020007686 W JP2020007686 W JP 2020007686W WO 2020175537 A1 WO2020175537 A1 WO 2020175537A1
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- Prior art keywords
- resin composition
- group
- mass
- resin
- compound
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 112
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 239000000805 composite resin Substances 0.000 title claims abstract description 17
- -1 prepreg Substances 0.000 title description 80
- 150000001875 compounds Chemical class 0.000 claims abstract description 109
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 53
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 30
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims description 47
- 229920005989 resin Polymers 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 25
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 23
- 239000000945 filler Substances 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 13
- 241001556567 Acanthamoeba polyphaga mimivirus Species 0.000 claims description 12
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 11
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 50
- 229920001955 polyphenylene ether Polymers 0.000 description 32
- 238000000034 method Methods 0.000 description 30
- 239000004643 cyanate ester Substances 0.000 description 29
- 239000011521 glass Substances 0.000 description 29
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 125000001424 substituent group Chemical group 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000002966 varnish Substances 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 15
- 150000001491 aromatic compounds Chemical class 0.000 description 15
- 239000011889 copper foil Substances 0.000 description 14
- 230000009477 glass transition Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000001723 curing Methods 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
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- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 0 *c1c(*)c(ON)c(*)c(*)c1-c(c(*)c1*)c(*)c(*)c1ON Chemical compound *c1c(*)c(ON)c(*)c(*)c1-c(c(*)c1*)c(*)c(*)c1ON 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- JKPSCLPFXNWYAW-UHFFFAOYSA-N CCCCCCCC.N#CO Chemical compound CCCCCCCC.N#CO JKPSCLPFXNWYAW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
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- 239000003063 flame retardant Substances 0.000 description 2
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- 125000005843 halogen group Chemical group 0.000 description 2
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- 229910003475 inorganic filler Inorganic materials 0.000 description 2
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
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- 229910000077 silane Inorganic materials 0.000 description 2
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- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
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- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
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- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
- B32B2305/076—Prepregs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Definitions
- Resin composition prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board
- the present invention relates to a resin composition, a prepreg using the same, a metal foil laminated layer board, a resin composite sheet, and a printed wiring board.
- Patent Document 1 discloses that a terminal vinyl compound (3) of a bifunctional phenylene ether oligomer having a polyphenylene ether skeleton, a specific maleimide compound (13), and a naphthol aralkyl type cyanate ester resin.
- a resin composition containing (O) and a novolac type epoxy resin ( ⁇ 0) modified with a naphthalene skeleton is disclosed.
- Patent Document 2 a resin having a maleimide group at least at one end (1 ⁇ 1, 1 ⁇ 1'-4, 4'-aminophenyl bismuthamide and an aminobismaleimide-based resin made of diamine as raw materials) And a flame-retardant resin group consisting of a brominated styrene represented by the formula ( ⁇ 1) and a copolymer of divinylbenzene represented by the formula ( ⁇ 2) ⁇ 2020/175 537 2020/007686
- a product is disclosed.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2 0 1 ⁇ -1 3 8 3 6 4
- Patent Document 2 Japanese Patent Laid-Open No. 03-060062993
- An object of the present invention is to solve such problems, and a resin composition having a low dielectric constant and a low dielectric loss tangent and high heat resistance, a prepreg using the same, a metal foil-clad laminate, and a resin.
- the purpose is to provide composite sheets and printed wiring boards.
- the present inventors have investigated the component composition of a resin composition that is particularly suitable for the use of printed wiring boards such as prepregs.
- the polyfunctional vinyl aromatic polymer and thermosetting compound have been obtained. It was found that the resin composition in which the combination of and showed a low dielectric constant and a low dielectric loss tangent and high heat resistance. However, it was found that these properties were inferior when a radical polymerization initiator was added.
- the present invention is ⁇ 2020/175 537 3 ⁇ (:171? 2020 /007686
- thermosetting compound (M) is a cyanato group, a vinyl group, a maleimide group, and a nadiimide group.
- thermosetting compound (Mitsumi) Any one of ⁇ 1> to ⁇ 3>, in which the content of the thermosetting compound (Mitsumi) is 5 to 95 parts by mass with respect to 100 parts by mass of the total amount of resin components in the resin composition.
- the content of the polyfunctional vinyl aromatic polymer () is 5 to 95 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition, ⁇ 1> to ⁇ 4. > The resin composition of any one of.
- ⁇ 7> The resin composition according to ⁇ 6>, in which the content of the filler ( ⁇ ) is 100 to 500 parts by mass with respect to 100 parts by mass of the total amount of resin components in the resin composition. ..
- ⁇ 9> at least one layer formed from the prepreg according to ⁇ 8>, and ⁇ 2020/175 537 4 ⁇ (:171? 2020 /007686
- a metal foil-clad laminate comprising a layer formed from the prepreg and a metal foil disposed on one side or both sides of the layer.
- a resin composite sheet comprising a support and a layer formed on the surface of the support and formed from the resin composition according to any one of ⁇ 1> to ⁇ 7>.
- a printed wiring board comprising an insulating layer and a conductor layer arranged on the surface of the insulating layer, wherein the insulating layer is any one of ⁇ 1> to ⁇ 7>.
- a printed wiring board comprising at least one of a layer formed from a resin composition and a layer formed from the prepreg according to ⁇ 8>.
- the present invention it is possible to provide a resin composition having a low dielectric constant and dielectric loss tangent and high heat resistance, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the same. ..
- the resin composition according to the present embodiment is characterized by containing a polyfunctional vinyl aromatic polymer () and a thermosetting compound (M) and not containing a radical polymerization initiator.
- the resin composition according to this embodiment is a thermosetting resin in which the thermosetting group of the polyfunctional vinyl aromatic polymer (8) or the thermosetting compound (M) is cured by heat. ⁇ 2020/175 537 5 ⁇ (:171? 2020 /007686
- Resin composition When such a resin composition does not contain a thermal radical polymerization initiator, the polymerization initiation temperature of the polyfunctional vinyl aromatic polymer () and the polymerization initiation temperature of the thermosetting compound (M) are close to each other, and It is considered that the vinyl aromatic polymer () and the thermosetting compound (M) can be sufficiently cured, and as a result, low dielectric constant, low dielectric loss tangent, and high heat resistance can be achieved. Further, by not containing the photo-radical polymerization initiator, the photo-curing of the polyfunctional vinyl aromatic polymer () and the thermosetting compound (M) can be effectively suppressed without shading during storage.
- the resin composition according to the present embodiment is preferably a non-photosensitive thermosetting resin composition that is not cured by light but is cured mainly by heat.
- the resin composition according to the present embodiment contains a polyfunctional vinyl aromatic polymer ().
- the polyfunctional vinyl aromatic polymer (8) is preferably a polymer obtained by polymerizing an aromatic compound having two or more vinyl groups in the molecule.
- the aromatic compound having two or more vinyl groups in the molecule may be, for example, any of the positional isomers of a vinyl group, or may be a mixture of such positional isomers. Good. More specifically, when the polyfunctional vinyl aromatic polymer (8) is an aromatic compound having two vinyl groups in the molecule, Body, O-body or a mixture of these positional isomers, It is preferably either the body or a mixture of these positional isomers.
- an aromatic compound having one or more vinyl groups As a monomer constituting the polyfunctional vinyl aromatic polymer (), an aromatic compound having one or more vinyl groups (hereinafter, an aromatic compound having two or more vinyl groups is (Also referred to as a vinyl aromatic compound), and an aromatic compound having one or two vinyl groups is preferable.
- a polyfunctional vinyl aromatic polymer () a structural unit (3) derived from an aromatic compound having two vinyl groups (also referred to as a divinyl aromatic compound) and an aromatic compound having one vinyl group Polymers containing derived structural units ⁇ 2020/175 537 6 ⁇ (:171? 2020 /007686
- the divinylaromatic compound forming the structural unit (3) is preferably a compound having a hydrocarbon aromatic ring, such as divinylbenzene, diallylbenzene, bis(vinyloxy)benzene, bis(1-methylvinyl).
- examples thereof include benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene and bis(4-allyloxyphenyl)fluorene. Of these, divinylbenzene is particularly preferable.
- the morphology in the polymer of the constitutional unit derived from the divinyl aromatic compound is such that only one of the (3 _ 1) vinyl groups undergoes a polymerization reaction and the other vinyl group remains unreacted.
- the polyfunctional vinyl aromatic compound (preferably divinyl aromatic compound) is an arbitrary substituent (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms) within the range that the effect of the present invention is exhibited. Group, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, an amino group, a carboxy group, a halogen atom, and the like).
- the structural unit (3) derived from the above polyfunctional vinyl aromatic compound (preferably divinyl aromatic compound) preferably contains a structural unit represented by the following formula (V).
- the aromatic hydrocarbon linking group may be a group consisting of only an aromatic hydrocarbon that may have a substituent, or an aromatic hydrocarbon that may have a substituent. ⁇ 2020/175 537 7 (:171? 2020/007686
- aromatic hydrocarbon a group consisting of other linking groups, and preferably a group consisting only of an aromatic hydrocarbon which may have a substituent.
- the substituents that the aromatic hydrocarbon may have include the above-mentioned substituents. Further, it is preferable that the aromatic hydrocarbon does not have a substituent.
- the aromatic hydrocarbon linking group is usually a divalent linking group.
- aromatic hydrocarbon linking group examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group and a fluorenediyl group which may have a substituent.
- a phenylene group which may have a substituent is preferable.
- substituents include the above-mentioned substituents, but it is preferable that the above-mentioned groups such as the phenylene group do not have a substituent.
- a structural unit (3) derived from a polyfunctional vinyl aromatic compound is a structural unit represented by the following formula (VI) and a structural unit represented by the following formula (V 2) It is more preferable to include a structural unit and at least one structural unit represented by the following formula (3): In addition, * in the following formula represents a bonding position.
- 1_ 1 is an aromatic hydrocarbon linking group (preferably the number of 6 to 2 2 carbon atoms, 6 to more preferably 1 8, more preferably 6 to 1 0).
- aromatic hydrocarbon linking group preferably the number of 6 to 2 2 carbon atoms, 6 to more preferably 1 8, more preferably 6 to 1 0.
- Specific examples thereof include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent.
- Preferred are phenylene groups.
- the substituent include the above-mentioned substituents, but the above-mentioned groups such as a phenylene group preferably have no substituent. ⁇ 2020/175 537 8 ⁇ (:171? 2020 /007686
- the polyfunctional vinyl aromatic polymer () may be a homopolymer of the structural unit (3) as described above, or may be a copolymer with the structural unit (digest) or the like. Good.
- the copolymerization ratio of the structural unit (3) is preferably 5 mol% or more, and more preferably 10 mol% or more. It is more preferably 15 mol% or more. The upper limit is practically 90 mol% or less.
- the polyfunctional vinyl aromatic polymer () is a copolymer containing a structural unit (shallow) derived from a monovinyl aromatic compound
- examples of the monovinyl aromatic compound include styrene and vinylnaphthalene.
- Vinyl aromatic compounds such as vinylbiphenyl; ⁇ -methylstyrene, -methylstyrene, -methylstyrene, ⁇ , Nuclear alkyl-substituted vinyl aromatic compounds such as dimethylstyrene, O-ethylvinylbenzene, 01-ethylvinylbenzene, _ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl are listed.
- the monovinyl aromatic compounds exemplified here may optionally have the above-mentioned substituents. These monovinyl aromatic compounds may be used alone or in combination of two or more.
- the constitutional unit derived from the monovinyl aromatic compound (the bowl) is preferably a constitutional unit represented by the following formula (4).
- 1_ 2 have the above substituent ⁇ 2020/175 537 9 ⁇ (:171? 2020 /007686
- the copolymerization ratio of the structural unit (shallow) is preferably 10 mol% or more, 1 It is more preferably at least 5 mol %.
- the upper limit is preferably 98 mol% or less, more preferably 90 mol% or less,
- the polyfunctional vinyl aromatic polymer () may have other structural units.
- the other structural unit include a structural unit ( ⁇ ) derived from a cycloolefin compound.
- the cycloolefin compound include hydrocarbons having a double bond in the ring structure.
- monocyclic cyclic refynes such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene
- compounds having a norbornene ring structure such as norbornene and dicyclopentagen
- aromatic rings such as indene and acenaphthylene were condensed.
- a cycloolefin compound etc. can be mentioned.
- Examples of norbornene compounds include those described in paragraphs 0 0 3 7 to 0 0 4 3 of JP-A No. 2018-39995, the contents of which are incorporated herein. ..
- the cycloolefin compounds exemplified here may further have the above-mentioned substituents.
- the copolymerization ratio of the structural unit ( ⁇ ) is preferably 10 mol% or more, 2 It is more preferably 0 mol% or more, and further preferably 30 mol% or more.
- the upper limit is preferably 90 mol% or less
- the polyfunctional vinyl aromatic polymer (8) may further incorporate a structural unit (O1) derived from a different polymerizable compound (hereinafter, also referred to as other polymerizable compound).
- a structural unit (O1) derived from a different polymerizable compound (hereinafter, also referred to as other polymerizable compound).
- Other polymerizable compounds (monomers) include, for example, 3 vinyl groups. ⁇ 2020/175 537 10 ⁇ (:171? 2020 /007686
- Compounds include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene and 1,2,4-trivinylcyclohexane.
- ethylene glycol diacrylate, butadiene, etc. may be mentioned.
- a structural unit derived from another polymerizable compound (copolymerization ratio of 0 is preferably 30 mol% or less, more preferably 20 mol% or less, and 10 mol% or less. Is more preferable.
- a polymer including the structural unit (3) as an essential component and including at least one of the structural units (distance) to ( ⁇ 0) is exemplified. Is exemplified by an embodiment in which the total of the structural units (3) to (0) accounts for 95 mol% or more, and more preferably 98 mol% or more of all the structural units.
- the constitutional unit (3) is essential, and the constitutional unit containing an aromatic ring is 90 mol% or more of all constitutional units excluding the end. Is preferable, more preferably 95 mol% or more, and even more preferably 100 mol%.
- one structural unit shall be derived from one molecule of the monomer that constitutes the multi-functional vinyl aromatic polymer ().
- the method for producing the polyfunctional vinyl aromatic polymer (8) is not particularly limited and may be a conventional method.
- a monomer containing a divinyl aromatic compound if necessary, a monovinyl aromatic compound, cycloolefin
- Compounds and the like and polymerizing in the presence of a Lewis acid catalyst.
- a Lewis acid catalyst metal fluoride or its complex can be used.
- the polyfunctional vinyl aromatic polymer (8) has a number average molecular weight IV! n of 30
- the upper limit is preferably 100,000 or less, more preferably 100,000 or less, further preferably 5,000 or less, and further preferably 4,000 or less. preferable.
- the monodispersity (Mw/Mn) represented by the ratio of the weight average molecular weight IV! and the number average molecular weight IV! n is preferably 100 or less, more preferably 50 or less, and more preferably 20 or less. It is more preferable that there is. It is practical that the lower limit value is 1.1 or more.
- the polyfunctional vinyl aromatic polymer (8) is preferably soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.
- the polyfunctional vinyl aromatic polymer () is described in the compounds described in paragraphs 0029 to ⁇ 058 of International Publication No. 2017/1 1 5813, the synthesis reaction conditions thereof, and the like.
- the content of the polyfunctional vinyl aromatic polymer () is preferably 5 parts by mass or more, and 10 parts by mass or more, when the total amount of the resin components in the resin composition is 100 parts by mass. It is more preferable that the amount is 15 parts by mass or more. ⁇ 2020/175 537 12 ⁇ (:171? 2020 /007686
- the amount is more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, and 60 parts by mass or more.
- the content of the polyfunctional vinyl aromatic polymer () is preferably the above lower limit value or more, particularly low dielectric constant can be effectively achieved.
- the upper limit of the content of the polyfunctional vinyl aromatic polymer () is preferably 95 parts by mass or less when the total amount of the resin components in the resin composition is 100 parts by mass. It is more preferably 0 parts by mass or less, further preferably 85 parts by mass or less, and further preferably 80 parts by mass or less.
- the polyfunctional vinyl aromatic polymer () may be contained in the resin composition in only one kind or in two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.
- the resin component includes a polyfunctional vinyl aromatic polymer (8), a thermosetting compound (M), and other resins described later.
- thermosetting compound (Mitsumi) means a thermosetting compound other than the polyfunctional vinyl aromatic polymer (8).
- the thermosetting compound (M) a cyana group, a vinyl group (however, a group that becomes a polyfunctional vinyl aromatic polymer, a maleimide group, and a nadiimide group are not included. A vinylphenyl group is preferable.), a maleimide group. Group, and a compound having at least one functional group selected from the group consisting of nadiimide groups are preferable, and a cyanate ester compound having a cyanato group (Min 1)
- a modified polyphenylene ether compound having a vinyl group (preferably a vinylphenyl group) (Minami 2), a maleimide compound having a maleimide group (Minami 3), and a nadiimide compound having a nadiimide group (Minami 4) are more preferable, Further, cyanate ester compounds having a cyanato group (Minami 1), modified polyphenylene ether compounds having a vinyl group (preferably vinylphenyl group) (Minami 2), and maleimide compounds having a maleimide group (Minami 3) are further included. preferable.
- the cyanate ester compound is a general term for compounds having a cyanato group.
- the cyanate ester compound (Mizu 1) used in the present invention preferably has one or more cyanato groups in one molecule, and more preferably has two or more cyanato groups. Further, the upper limit of the number of cyanato groups in one molecule of the cyanate ester compound (N 1) is preferably 12 or less, and more preferably 10 or less. Further, the cyanato group of the above-mentioned cyanate ester compound (Minami 1) is preferably a cyanato group directly bonded to the aromatic ring.
- Examples of the cyanate ester compound (Mitsumi 1) include naphthol aralkyl type cyanate ester compound (naphthol aralkyl cyanate), naphthylene ether type cyanate ester compound, phenol novolac type cyanate ester compound, and biphenyl aralkyl type. Cyanate ester compound, bisphenol octane cyanate ester compound, diallyl bisphenol octane cyanate ester compound, bisphenol IV!
- At least one selected from the group consisting of an ester compound and an adamantane skeleton type cyanate compound is included.
- at least one selected from the group consisting of naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, and xylene resin type cyanate ester compounds is preferable, and naphthol aralkyl type cyanate compounds are preferable. More preferably, it is an acid ester compound.
- These cyanate ester compounds may be prepared by known methods, or commercially available products may be used.
- Examples of the cyanate ester compound (N 1) include a naphthol aralkyl type cyanate ester compound represented by the following formula (3 1).
- the naphthol aralkyl-type cyanate compound represented by the formula (31) is Naphthol or naphthols such as /3-naphthol and -xylylene glycol, It is obtained by condensing a naphthol aralkyl resin obtained by the reaction with «, -dimethoxy- -xylene, 1, 4-di(2-hydroxy _ 2-propyl) benzene, etc. and a halogenated cyanide. ..
- the manufacturing method is not particularly limited. ⁇ 2020/175 537 14 ⁇ (:171? 2020 /007686
- the thermosetting compound (N) is preferably a modified polyphenylene ether compound (N 2) which is end-modified with a substituent having a vinyl group (preferably vinyl phenyl group).
- the modified polyphenylene ether compound (N2) used in the present invention preferably has one or more vinyl groups in one molecule, and more preferably has two or more vinyl groups. Further, the upper limit of the number of vinyl groups in one molecule of the modified polyphenylene ether compound (N 2) is preferably 5 or less, and more preferably 3 or less.
- the modified polyphenylene ether compound (Mimi 2) is, for example, a modified product in which all or part of the terminals of polyphenylene ether is terminally modified with a vinyl group or a vinylphenyl group.
- the “polyphenylene ether” referred to in the present specification refers to a compound having a polyphenylene ether skeleton represented by the following formula (X I).
- [3 ⁇ 4 24 , [3 ⁇ 4 25 , [3 ⁇ 4 26 , and [3 ⁇ 4 27, which may be the same or different, represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom. ..
- the symbol represents the bonding position.
- the modified polyphenylene ether may further include a repeating unit represented by the formula (2) or the formula (3).
- 3 may be the same or different and is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group.
- the symbol represents the bonding position.
- [3 ⁇ 4 36 , [3 ⁇ 4 37 , [3 ⁇ 4 38 , [3 ⁇ 4 39 , [3 ⁇ 4 40 , [3 ⁇ 4 41 , [3 ⁇ 4 42 , [3 ⁇ 4 43, may be the same or different, a hydrogen atom, An alkyl group or phenyl group having 6 or less carbon atoms. Is a linear, branched or cyclic divalent hydrocarbon having 1 to 20 carbon atoms. * Represents a bonding position.
- the modified polyphenylene ether compound (Mitsumi 2) is partially or entirely ⁇ 2020/175 537 16 ⁇ (: 171-1? 2020/007686
- a modified polyphenylene ether functionalized with an ethylenically unsaturated group such as a rubenzyl group, an epoxy group, an amino group, a hydroxy group, a mercapto group, a carboxy group, and a silyl group can also be used. These may be used alone or in combination of two or more. Examples of the polyphenylene ether having a hydroxy group at its end include 389,900 manufactured by Innovative Plastics Co., Ltd.
- the method for producing the modified polyphenylene ether compound is not particularly limited as long as the effects of the present invention can be obtained.
- the bifunctional phenylene ether oligomer and vinylbenzyl chloride are dissolved in a solvent, and a base is added under heating and stirring to react them, and then the resin is solidified. It can be manufactured.
- Those functionalized with a carboxy group are produced, for example, by melt-kneading an unsaturated carboxylic acid or a functionalized derivative thereof with polyphenylene ether in the presence or absence of a radical initiator and reacting them. It Alternatively, it is produced by dissolving a polyphenylene ether and an unsaturated carboxylic acid or a functional derivative thereof in an organic solvent in the presence or absence of a radical initiator, and reacting in a solution.
- the modified polyphenylene ether compound (M2) is a modified polyphenylene ether having at least one terminal (preferably both terminals) having an ethylenically unsaturated group (hereinafter, referred to as "modified polyphenylene ether (9 )” may be included).
- modified polyphenylene ether (9 ) examples include ethenyl group, allyl group, acryloyl group, methacryloyl group, probenyl group, butenyl group, alkenyl group such as hexenyl group and octenyl group, cycloalkenyl group such as cyclopentenyl group and cyclohexenyl group.
- alkenylaryl groups such as vinylphenyl group, vinylbenzyl group and vinylnaphthyl group.
- the two ethylenically unsaturated groups at both ends may have the same functional group or different functional groups.
- the modified polyphenylene ether (9) includes a structure represented by the formula (1). ⁇ 0 2020/175 537 17 (: 17 2020 /007686
- X 3 represents an aromatic group
- ( ⁇ 3- ⁇ ) 01 represents a polyphenylene ether moiety
- [3 ⁇ 4 2 and 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group
- 01 represents a number of 1 to 100
- n represents a number of 1 to 6, and 1 to 4 Represents the number of.
- X 3 represents an aromatic group
- ( ⁇ 3- ⁇ ) 01 represents a polyphenylene ether moiety
- [3 ⁇ 4 2 and 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group
- 01 represents a number of 1 to 100
- n represents a number of 1 to 6
- 1 to 4 Represents the number of.
- X 3 represents an aromatic group
- ( ⁇ 3- ⁇ ) 01 represents a polyphenylene ether moiety
- [3 ⁇ 4 2 and 3 each independently represent a hydrogen atom, an alkyl group,
- n is a number of 1 or more and 4 or less, more preferably 1 or 2, and more preferably 1 or 2.
- n is preferably a number of 1 or more and 3 or less, more preferably 1 or 2, and even more preferably 2.
- N and 9 may be different from each other.
- the modified polyphenylene ether (9) is preferably represented by the formula (2).
- one (X1X-X)1 is represented by the formula (3) or the formula (4).
- Two or more kinds of compounds different in 3 and 13 may be contained. ⁇ 2020/175 537 18 ⁇ (:171? 2020 /007686
- 11 may be the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. [3 ⁇ 4 7 , They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. The symbol represents the bonding position.
- [3 ⁇ 4 12 , [3 ⁇ 4 13 , [3 ⁇ 4 14 , ][ 3 ⁇ 4 15 , [3 ⁇ 4 16 , [3 ⁇ 4 17 , [3 ⁇ 4 18 , and 3 ⁇ 4 19 may be the same or different, a hydrogen atom, An alkyl group or a phenyl group having 6 or less carbon atoms. Is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. * Represents a bonding position.
- the (1)-(1) in the formula (2) is represented by the formula (5).
- [3 ⁇ 4 22 and [3 ⁇ 4 23, which may be the same or different, are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
- [ 21 may be the same or different and each represents an alkyl group having 6 or less carbon atoms or a phenyl group.
- Equation (4) for example, methylene, ethylidene, 1 - methylcarbamoyl Ruechiriden, 1, 1 - propylidene, 2, 2-propylidene, 1, 4-off Enirenbisu (1 - methylethylidene) 1
- examples thereof include, but are not limited to, divalent organic groups such as 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene.
- Phenylene ether is preferable, and in particular, one represented by formula (3) or formula (4) ( ⁇ 1 X — ⁇ ) is represented by formula (9), formula (1 0), and/or formula (1 1 ), and one ( ⁇ 110) one represented by the formula (5) is the formula (1 2) or the formula (1 3), or the formula (1 2) and the formula (1 3) are random. It is more preferable that the structure has a structure in which
- [3 ⁇ 445, [ ⁇ 46, [3 ⁇ 4, which may be the same or different, are a hydrogen atom or a methyl group.
- Eighty- two is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. * Is the binding position.
- Specific examples of eighty- two in the formulas (10) and (11) are the same as the eighteenth one in the formula (4). ⁇ 2020/175 537 20 (:171? 2020/007686
- the modified polyphenylene ether compound (Mitsumi 2) has a polystyrene-reduced number average molecular weight of 5,000 or more and 3,000 or less according to the method.
- the number average molecular weight is at least the above lower limit, the stickiness tends to be further suppressed when the resin composition of the present embodiment is formed into a coating film.
- the solubility in a solvent tends to be further improved.
- the modified polyphenylene ether compound (Mimi 2) preferably has a polystyrene-equivalent weight average molecular weight of 800 or more and 100 or less, and 800 or more and 500 or less. Is more preferable.
- the dielectric constant and dielectric loss tangent of the resin composition tend to be lower, and when the content is less than the above upper limit, solubility in a solvent, low viscosity and moldability Tend to improve.
- the carbon-carbon unsaturated double bond equivalent at the terminal of the modified polyphenylene ether compound (Mitsumi 2) is preferably 400 to 500 0.99 per carbon-carbon unsaturated double bond, It is more preferable that it is 4 0 9 ⁇ 2 5 0 0 9.
- the method for producing the modified polyphenylene ether compound is not particularly limited, and for example, a bifunctional phenol compound and a monofunctional phenol compound are subjected to acid coupling to obtain a bifunctional phenylene ether oligomer. It can be produced by a step (oxidation coupling step) and a step of vinylbenzyl etherifying the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer (vinyl benzyl etherification step). Further, as such a modified polyphenylene ether compound (Minami 2), for example, Mitsubishi Gas Chemical Co., Inc. ( ⁇ Miichi 1 2 3 1:1 2 0 0 etc.) can be used.
- a maleimide compound (Mimi 3) is a compound that has one or more maleimide groups in the molecule. ⁇ 2020/175 537 21 ⁇ (: 171-1? 2020 /007686
- the maleimide compound (3) used in the present invention preferably has one or more maleimide groups in one molecule, more preferably two or more.
- the upper limit of the number of maleimide groups in one molecule of the maleimide compound (Mitsumi 3) is preferably 15 or less, and more preferably 13 or less.
- bismaleimide compounds and polymaleimide compounds having two or more maleimide groups in the molecule are preferable, and 4,4'-diphenylmethane maleimide, 4,4'-diphenyl ether bismaleimide, 01— Phenylene bismaleimide,
- the compound is a compound containing a structural unit represented by any one of the following formulas (31) to (34): 1,6-bismaleimidane (2,2,4-trimethyl)hexane.
- n 1 is a number of 1 to 10, and a number of 1 to 4 is more preferable. Two or more compounds having different n 1 may be contained.
- Each 7 independently represents a hydrogen atom or a methyl group.
- 1 to 3 are methyl groups and the remaining 3 to 1 are ethyl groups. Of these, two are more preferably methyl groups, and the remaining two are more preferably ethyl groups. In addition, each of the two aromatic rings is substituted.
- equivalents of unsaturated imide groups maleimide de Compound (Snake 3) is preferably from 2 0 0 9/6 9 than on, also 4 0 0 Preferably 9 or less
- the equivalent here is the weighted average equivalent of unsaturated imide groups in consideration of the mass of each maleimide compound contained in the resin composition.
- the nadiide compound (Mimi 4) is a compound having a nadiide group in its molecule. It is preferable that the nadiimide compound (Minami 4) used in the present invention has one or more nadiimide groups in one molecule, and more preferably two or more. Further, the upper limit of the number of nadiimide groups in one molecule of the nadiide compound (N 4) is preferably 5 or less, and more preferably 3 or less. More specifically, it is preferable that the namidide compound (Minami 4) has a group represented by the following formula (N 1) or (N 2 ). The symbol represents the bonding position.
- nadiimide compound a compound represented by the following formula (N 3) is more preferable. ⁇ 0 2020/175537 24 ?01/1?2020/007686
- Examples of the divalent linking group containing an aromatic ring include a phenylene group, a biphenylene group and a naphthylene group.
- the content of the thermosetting compound (M) is preferably 5 parts by mass or more based on 100 parts by mass of the resin component in the resin composition according to the present embodiment, and 10 parts by mass. It is more preferably at least 15 parts by mass, more preferably at least 15 parts by mass, still more preferably at least 20 parts by mass.
- the upper limit is preferably 95 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less.
- the upper limit value is preferably 1900 parts by mass or less, more preferably 900 parts by mass or less, further preferably 400 parts by mass or less, and 120 parts by mass or less. Or may be 80 parts by mass or less, or 60 parts by mass or less.
- the resin composition may contain only one thermosetting compound (Mitsumi),
- the resin component occupy 90% by mass or more of the resin composition (when ⁇ is not contained, the amount is 95% by mass or more). Is more preferable, and it is still more preferable that it accounts for 98% by mass or more.
- the resin component preferably accounts for 15% by mass or more of the resin composition, and more preferably 20% by mass or more. It is more preferable that the amount of this component be 30% by mass or more. Further, as the upper limit value, it is preferable that the resin component accounts for 90% by mass or less of the resin composition, more preferably 85% by mass or less, and further preferably 80% by mass or less.
- the resin composition according to this embodiment does not contain a radical polymerization initiator.
- "does not contain” means not to be positively mixed, and does not mean that impurities and the like are mixed unintentionally.
- impurities when impurities are mixed unintentionally, it is, for example, not more than 401, and even less than 1 on a mass basis. In the present invention, it is preferably 0.
- the type of radical polymerization initiator is not particularly limited, and examples thereof include a thermal radical polymerization initiator and a photo radical polymerization initiator.
- radical polymerization initiator examples include peroxides, azo compounds, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, and phosphinoxide compounds.
- peroxides examples include compounds having a peroxy group (10,101) in the molecule, and compounds having a 1-butylperoxy group, a compound having a cumylperoxy group, and a compound having a benzoylperoxy group are preferable. .. Specific examples include benzoyl peroxide (M), _ chlorobenzoyl peroxide, dicumyl peroxide ( ⁇ 1), di_1-butylperoxide, diisopropylperoxycarbonate, 2,5-dimethyl- twenty five - ⁇ 2020/175 537 26 ⁇ (:171? 2020 /007686
- 5-D-I-butylperoxyhexane may be mentioned.
- Commercially available products include Perbutyl! I, Perbutyl, Perbutyl, Parkmill! I, Parkmill, Parkmillo, Perocta! I, Perhexa 25, manufactured by NOF CORPORATION.
- 2,3-dimethyl-2,3-diphenylbutane is also mentioned as a radical polymerization initiator.
- examples of commercially available products include Nofmer Mitsumi 910.
- the radical polymerization initiator described in paragraph 0 042 of International Publication No. WO 201 3/0 4 7 3 05 is also exemplified, and the contents thereof are incorporated in the present specification.
- the resin composition according to this embodiment may be configured not to contain a cationic polymerization initiator.
- the resin composition according to the present embodiment may be configured to contain no photopolymerization initiator.
- the resin composition according to the present embodiment preferably contains a filler ( ⁇ 3) in order to improve low dielectric constant, low dielectric loss tangent, flame resistance and low thermal expansion, and an inorganic filler is preferable.
- a filler ( ⁇ 3) used a known filler can be appropriately used, and the type thereof is not particularly limited, and those generally used in the art can be preferably used. Specifically, natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica and other silicas, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, nitride.
- metal hydrate such as magnesium hydroxide, molybdenum compound such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, Mica, Mina Glass, Eight Glass, Mitsu Glass, O Glass,! _—Glass, Glass, 3-Glass, IV!-Glass 0 200, short glass fibers (including fine glass powders such as Mitsu Glass, Cho Glass, 0 glass, 3 glass, 0 glass), hollow glass, spherical glass, etc.
- inorganic fillers styrene-type, butadiene-type, acrylic-type rubber powders, core-shell type rubber powders, silicone resin powders, silicone rubber powders, organic fillers such as silicone composite powders, and the like can be mentioned.
- silica aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are preferable, and silica is more preferable.
- the silica is preferably spherical silica.
- the spherical silica may also be hollow silica.
- the content of the filler ( ⁇ in the resin composition according to the present embodiment can be appropriately set according to the desired characteristics, and is not particularly limited, but the total amount of the resin components in the resin composition is 1 In the case of XX parts by mass, it is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, and 50 parts by mass or more.
- the upper limit is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, further preferably 300 parts by mass or less, and 25
- the content is more preferably 0 parts by mass or less, and may be 200 parts by mass or less.
- the filler ( ⁇ 3) may be used singly or in combination of two or more. In that case, the total amount is preferably within the above range.
- the resin composition according to the present embodiment is a polyfunctional vinyl aromatic polymer (8 ⁇ 2020/175 537 28 ⁇ (:171? 2020 /007686
- thermosetting compound (Mitsumi)
- other resin components may be included.
- the other resin component include one or more selected from the group consisting of epoxy resin, phenol resin, oxetane resin, benzoxazine compound, compound having a polymerizable unsaturated group, elastomer and active ester compound.
- the total content of the polyfunctional vinyl aromatic polymer () and the thermosetting compound (M) in the resin component is preferably 50% by mass or more, It is preferably 0% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 95% by mass or more, 97% by mass. It may be more than 90% by mass.
- the resin composition according to this embodiment may further include a curing accelerator.
- the curing accelerator is not particularly limited, and examples thereof include organic metal salts (for example, zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetoneacetone, nickel octylate, manganese octylate, etc.), Phenol compounds (eg phenol, xylenol, cresol, resorcin, catechol, octylphenol, nonylphenol etc.), alcohols (eg 1-butanol, 2-ethylhexanol etc.), imidazoles (eg 2-methylimidazole) , 2-ethyl-4-methylimidazole,
- organic metal salts for example, zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetoneacetone, nickel o
- 2-phenyl imidazole 1-cyanoethyl-2-phenyl imidazole, 1-cyanoethyl-2-ethyl-4-methyl imidazole, 2-phenyl-4,5-dihydroxymethyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, etc.
- imidazoles such as carboxylic acids or adducts of their acid anhydrides, amines (eg, dicyandiamide, benzyldimethylamine, 4-methyl-1 ⁇ 1, 1 ⁇ 1 _dimethylbenzylamine, etc.) ), phosphorus compounds (eg, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine compounds ⁇ 2020/175 537 29 ⁇ (:171? 2020 /007686
- Preferred curing accelerators are imidazoles and organic metal salts, with imidazoles being more preferred.
- the lower limit is preferably 0.005 parts by mass or more based on 100 parts by mass of the total amount of the resin components in the resin composition. , 0.01 parts by mass or more is more preferable, and 0.1 parts by mass or more is further preferable.
- the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, and 5 parts by mass or less based on 100 parts by mass of the total amount of the resin components in the resin composition. Is more preferable, and even more preferably 2 parts by mass or less.
- the curing accelerators may be used alone or in combination of two or more. When using 2 or more types, the total amount is within the above range.
- the resin composition according to this embodiment may contain a solvent, and preferably contains an organic solvent.
- the resin composition according to the present embodiment is in a form (solution or varnish) in which at least a part, preferably all of the various resin components described above are dissolved or compatible with a solvent.
- the solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent capable of dissolving or compatibilizing at least a part, preferably all, of the various resin components described above, and examples of the polar organic solvent include: , Ketones (eg, acetone, methyl ethyl ketone, methyl isoptyl ketone, etc.), cellosolves (eg, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (eg, ethyl lactate, methyl acetate, ethyl acetate, Butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.) Amides (for example, dimethoxyacetamide, dimethylformamides, etc.), and nonpolar organic solvents include And aromatic hydrocarbons (eg, toluene,
- the solvents may be used alone or in combination of two or more. ⁇ 02020/175537 30 ⁇ (: 17 2020 /007686
- the resin composition according to the present embodiment contains, in a range that does not impair the effects of the present invention, a flame retardant, an ultraviolet absorber, an antioxidant, a fluorescent whitening agent, a photosensitizer, a dye, a pigment, in addition to the above components. , A thickener, a flow control agent, a lubricant, an antifoaming agent, a dispersant, a leveling agent, a brightening agent, a polymerization inhibitor, a silane coupling agent, etc. These additives may be used alone or in combination of two or more.
- the resin composition according to the present embodiment is...! .6 ⁇ !
- the dielectric constant (01 ⁇ ) at 10°C 1 to 12 can be 2.6 or less, or 2.5 or less.
- the ideal lower limit of the dielectric constant is 1.0, but 2.1 or more is practical.
- the resin composition according to the present embodiment is...! .6 ⁇ !
- the dielectric loss tangent (0 degree) at 10 ⁇ 1 to 12 can be ⁇ .0030 or less, and can also be ⁇ .0025 or less. Yes, it can be less than 0.0000, or less than 0.0015.
- the lower limit of the dielectric constant is ideally 0, but practically 0.0001 or more.
- the dielectric constant and the dielectric loss tangent are measured by the methods described in Examples below.
- a low coefficient of thermal expansion (Octomi) can be realized.
- Octomi a low coefficient of thermal expansion
- ⁇ Cho ( ⁇ !/. ⁇ ) defined in 19 above it is preferably 75 or less, more preferably 72 or less, and even more preferably 70 or less.
- the lower limit is not particularly limited, but it is practically 50 or more.
- the resin composition according to the present embodiment is...! .6 ⁇ !
- the glass transition temperature can be 230° ⁇ or higher, 235° ⁇ or higher, and 240 ° ⁇ or higher. .. Above the glass transition temperature ⁇ 2020/175 537 31 ⁇ (:171? 2020 /007686
- Kirichi is not specifically limited, 4 0 0 ° ⁇ less, further, 3 5 0 ° ⁇ hereinafter is practical.
- the resin composition according to this embodiment has a glass transition temperature of 1% by mass of the resin component contained in the resin composition when formed into a plate-like cured product having a thickness of 1.6! Formed from a resin composition containing an amount of a thermal radical polymerization initiator (for example, Papillyl (trade name) manufactured by NOF CORPORATION) 1.
- the glass transition temperature of the plate-shaped cured product is preferably 8 ° or higher, more preferably 10° or higher.
- the upper limit is, for example, 25° or less.
- the glass transition temperature is measured by the method described in Examples below.
- the resin composition according to this embodiment can be manufactured by a conventional method. For example, a mode in which the polyfunctional vinyl aromatic polymer (8) and the thermosetting compound (Mitsumi) are mixed can be mentioned. The preferable content at this time is as described above.
- kneading and the like may be performed by appropriately coexisting the filler ( ⁇ ), other resin components, and other additives. By adding other resin components, the appearance may be improved or other characteristics may be improved.
- An example of the resin composition according to this embodiment is a varnish containing a solvent.
- Another example of the resin composition according to the present embodiment is a plate-shaped cured product or film.
- the resin composition according to this embodiment is preferably used for the applications described below.
- the resin composition according to this embodiment can be used as a cured product.
- the resin composition of the present embodiment can be preferably used as a low dielectric constant material and/or a low dielectric loss tangent material, as an insulating layer of a printed wiring board, or as a semiconductor package material.
- the resin composition of the present embodiment includes a prepreg, a metal foil-clad laminate formed from the prepreg, a resin composite sheet, and a printed wiring. ⁇ 2020/175 537 32 ⁇ (:171? 2020 /007686
- the thickness thereof is preferably 501 or more, more preferably 10 or more.
- the upper limit is preferably 201 01 or less, more preferably 110 11 111 or less.
- the thickness of the layered molded article means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated in the glass cloth or the like.
- a molded product such as a film formed from the resin composition according to the present embodiment may be used for the purpose of exposing and developing to form a pattern, or may be used for the purpose of not exposing and developing. In particular, it is suitable for applications not exposed to light and developed.
- the prepreg according to the preferred embodiment is formed from a base material (prepreg base material) and the resin composition according to the present embodiment.
- a base material prepreg base material
- the resin composition according to the present embodiment is applied (eg, impregnated or applied) to a base material, it is heated (eg, 120 to 220 °° C. for 2 to It is obtained by semi-curing by a method of drying for 15 minutes, etc.).
- the amount of the resin composition attached to the base material that is, the amount of the resin composition (including the filler) with respect to the total amount of the prepreg after semi-curing is preferably in the range of 20 to 99% by mass.
- the substrate is not particularly limited as long as it is a substrate used for various printed wiring board materials.
- the material for the base material include glass fiber (for example, glass, glass, ro glass, !_ glass, 3 glass, cho glass, glass, 11 1 ⁇ 1 glass, glass, spherical glass, etc.) and glass other than glass.
- Inorganic fibers eg, quartz
- organic fibers eg, polyimide, polyamide, polyester, liquid crystal polyester, etc.
- the form of the base material is not particularly limited, and examples thereof include a base material composed of layered fibers such as woven cloth, non-woven cloth, mouth roving, chopped strand mat, and surf essing mat.
- a substrate composed of long fibers such as glass cloth is preferable.
- the long fiber means, for example, that the number average fiber length is 6 The above is said.
- These base materials may be used alone or ⁇ 2020/175 537 33 ⁇ (:171? 2020 /007686
- woven fabrics that have undergone super-opening treatment and filling treatment are preferable from the viewpoint of dimensional stability, and silane coupling such as epoxy silane treatment and amino silane treatment from the viewpoint of moisture absorption heat resistance.
- a glass woven fabric whose surface is treated with an agent is preferable, and from the viewpoint of electrical characteristics, it is made of glass fiber having low dielectric constant and low dielectric loss tangent such as 1_ _ glass, _ glass, and _ glass. Dielectric glass cloth is preferred.
- the thickness of the base material is not particularly limited, and may be, for example, 0.01 to 0.1. It may be a degree.
- the metal foil-clad laminate according to a preferred embodiment includes at least one layer formed of the prepreg of the present embodiment and a metal foil arranged on one side or both sides of the layer formed of the prepreg.
- the metal foil-clad laminate of the present embodiment is produced, for example, by a method in which at least one prepreg of the present embodiment is arranged (preferably two or more prepregs), and a metal foil is arranged on one side or both sides of the prepreg to laminate-mold. Can be manufactured. More specifically, it can be produced by arranging a metal foil of copper, aluminum or the like on one or both sides of the prepreg and laminating and molding.
- the number of prepreg sheets is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 7 sheets.
- the metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foil such as rolled copper foil and electrolytic copper foil.
- the thickness of the copper foil is not particularly limited, and may be about 1.5 to 70.
- Examples of the molding method include methods commonly used for molding laminated boards and multilayer boards for printed wiring boards, and more specifically, multi-stage press machines, multi-stage vacuum press machines, continuous molding machines, autoclape molding machines. Etc., the temperature is about 180 ⁇ 350, the heating time is about 100 ⁇ 300 minutes,
- a multilayer board can be obtained by laminating and molding the prepreg of the present embodiment and a wiring board for an inner layer (also referred to as an inner layer circuit board) separately manufactured.
- Examples of the method for manufacturing a multilayer board include, for example, about 35 copper foils on both sides of one prepreg of this embodiment. ⁇ 2020/175 537 34 ⁇ (:171? 2020 /007686
- an inner layer circuit is formed, and blackening treatment is performed on this circuit to form an inner layer circuit board.
- a multilayer board can be produced.
- the metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.
- a printed wiring board is a printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer, wherein the insulating layer is formed from the resin composition according to the present embodiment. At least one of the formed layer and the layer formed from the prepreg according to the above embodiment is included.
- Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. An example of a method for manufacturing a printed wiring board will be shown below. First, a metal foil-clad laminate such as the copper foil-clad laminate described above is prepared. Next, the surface of the metal foil-clad laminate is subjected to an etching treatment to form an inner layer circuit, thereby manufacturing an inner layer substrate.
- a surface treatment is performed on the surface of the inner layer circuit of this inner layer substrate to increase the adhesive strength, then the required number of the above-mentioned prepregs are layered on the inner layer circuit surface, and the outer layer metal for outer layer circuit is placed on the outer side.
- the foils are laminated and heated and pressed to integrally mold them. In this way, a multilayer laminate having an insulating layer made of a base material and a cured product of a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit.
- a plated metal film is formed on the wall surface of the holes to electrically connect the inner layer circuit and the metal foil for the outer layer circuit, and then the outer layer.
- a printed wiring board is manufactured by forming an outer layer circuit by etching a metal foil for a circuit.
- the printed wiring board obtained in the above Production Example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment described above. Becomes That is, the prepreg of the present embodiment described above (for example, formed from the base material and the resin composition of the present embodiment impregnated or applied thereto) ⁇ 2020/175 537 35 ⁇ (:171? 2020 /007686
- the layer formed from the resin composition of the metal foil-clad laminate of the present embodiment described above serves as the insulating layer of the present embodiment.
- the resin composite sheet according to a preferred embodiment includes a support and a layer formed on the surface of the support and formed from the resin composition according to the present embodiment.
- the resin composite sheet can be used as a build-up film or a dry film solder resist.
- the method for producing the resin composite sheet is not particularly limited. For example, a solution obtained by dissolving the resin composition of the present embodiment described above in a solvent is applied to a support (coating) and dried to obtain a resin composite sheet. One method is to obtain a seat.
- Examples of the support used here include a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a release agent applied on the surface of these films.
- Release film organic film substrate such as polyimide film, conductor foil such as copper foil and aluminum foil, glass plate, 3 11 3 plate, Examples thereof include plate-shaped ones, but are not particularly limited.
- Examples of the coating method include a method in which a solution prepared by dissolving a resin composition in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator or the like.
- the support may be peeled off or etched from the resin composite sheet in which the support and the resin composition are laminated to obtain a single-layer sheet.
- the support can be used by forming a sheet by supplying the solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-like cavity and drying it. It is also possible to obtain a single layer sheet.
- the drying conditions for removing the solvent are not particularly limited, but the solvent tends to remain in the resin composition at low temperature, and the resin composition at high temperature. since the curing of the object progresses, preferably 2 0 ° ⁇ _ ⁇ 2 0 0 ° at ⁇ temperature 1-9 0 min.
- the resin composition ⁇ 2020/175 537 36 ⁇ (:171? 2020 /007686
- the product can be used in an uncured state by just drying the solvent, or can be used in a semi-cured (staged) state if necessary.
- the thickness of the resin layer of the resin composite sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited, but generally the coating thickness is large. If so, the solvent is likely to remain during drying, so that the range of 0.1 to 500 is preferable.
- the measurement was performed at 23 ° .
- Divinylbenzene 2 .25 mol (2 92.9), ethylvinylbenzene 1 .3 2 mol (1 72.0), styrene 1 1 .4 3 mol (1 1 10.9 0.39), acetic acid 11 -Propyl 15.0 mol (153 32.0 9 ) was charged into the reactor, and 600 mmol of diethyl ether complex of boron trifluoride was added at 70 ° and reacted for 4 hours. It was After stopping the polymerization solution with an aqueous solution of sodium hydrogen carbonate, the oil layer was washed with pure water three times and degassed under reduced pressure at 60 ° to recover a polyfunctional vinylbenzene polymer (3). The obtained polyfunctional vinylbenzene polymer (3) was weighed, and it was confirmed that the polyfunctional vinylbenzene polymer (3) 860.89 was obtained. ⁇ 2020/175 537 37 ⁇ (:171? 2020 /007686
- Structural units derived from divinylbenzene 209 mol% (24.3% by mass)
- Structural units derived from ethylvinylbenzene 9.1 mol% (10.7% by mass)
- Structural units derived from styrene 70. 0 mol% (65.0 mass%)
- the constitutional unit having a residual vinyl group derived from divinylbenzene was 16.7 mol% (18.5% by mass).
- a solvent was evaporated from the obtained varnish to obtain a mixed resin powder.
- the mixed resin powder is filled in a mold with a side of 100 ⁇ ! ⁇ ! and a thickness of 1.60101, and 1 2 copper foil (3M (3-1 ⁇ /13-1_?, Mitsui Mining & Smelting Co., Ltd.) Ltd.) were placed, pressure 30 1 ⁇ 9 / Rei_rei_1 2 and vacuum press 1 for 20 minutes at a temperature 220 ° ⁇ ,
- biphenyl aralkyl type maleimide 25 parts by weight of biphenyl aralkyl type maleimide is set to 12.5 parts by weight, and a phenyl ether type maleimide (manufactured by K.I Kasei Co., Ltd., 1 1//1 -80 (trade name))
- Example 1 A varnish was obtained in the same manner as in Example 1 except that 12.5 parts by mass was added. From the obtained varnish, in the same manner as in Example 1, 1. A thick cured plate was obtained. Obtained 1.6 The thick cured plate was evaluated for physical properties and the like according to the methods described below.
- a varnish was obtained in the same manner as in Example 1 except that 1 part by mass of a thermal radical polymerization initiator (Palptyl (trade name) manufactured by NOF CORPORATION) was added. From the obtained varnish, in the same manner as in Example 1, 1. A thick cured plate was obtained. With respect to the obtained 1-thick cured plate, physical properties and the like were evaluated according to the methods described below.
- a thermal radical polymerization initiator Palptyl (trade name) manufactured by NOF CORPORATION
- a varnish was obtained in the same manner as in Example 4 except that 1 part by mass of a thermal radical polymerization initiator (Palptyl (trade name) manufactured by NOF CORPORATION) was added. From the obtained varnish, in the same manner as in Example 4, 1. A thick cured plate was obtained. With respect to the obtained 1-thick cured plate, physical properties and the like were evaluated according to the methods described below.
- a thermal radical polymerization initiator Palptyl (trade name) manufactured by NOF CORPORATION
- Example 3 A varnish was obtained in the same manner as in Example 5, except that 1 part by mass of a thermal radical polymerization initiator (Palpyl P (trade name) manufactured by NOF CORPORATION) was added. A 1.6 mm thick cured plate was obtained from the obtained varnish in the same manner as in Example 5. The obtained 1.6 mm-thick cured plate was evaluated for physical properties according to the methods described below.
- a thermal radical polymerization initiator Palpyl P (trade name) manufactured by NOF CORPORATION
- the dielectric constant (D k) and dielectric loss tangent (D f) at 10 GHz of the obtained test piece from which the copper foil of the 1.6 mm thick cured plate was removed by etching were used.
- the measurement temperature was 23 ° C.
- the copper foil peel strength (adhesive strength) was measured twice in accordance with JIS C6481 5.7 “Peeling strength”, and the average value was obtained. ..
- the measurement temperature was 23 ° C.
- the glass transition temperature (T g) of the test piece obtained by removing the copper foil of the obtained 1.6 mm thick cured plate by etching is in accordance with JIS C 6481 5. 1 7. 2 It was measured by a DMA (Dynamic Mechanical Analysis) bending method with an analyzer. The glass transition temperature was estimated from the obtained chart of t a n 5.
- the coefficient of thermal expansion of the cured plate was measured by the TMA method (Thermo-Mechanical Analysis) specified in JIS C 6481 5.19, and the value was obtained. Specifically, of the cured plate obtained above ⁇ 2020/175 537 41 ⁇ (: 171-1? 2020/007686
- Glass transition temperature Glass transition temperature estimated from 1 3 n 5 measured by mouth 1 ⁇ /1 method
Abstract
Provided are a resin composition having a low dielectric constant and dielectric dissipation factor and high heat resistance, and a prepreg, a metal foil-clad laminate board, a resin composite sheet, and a printed circuit board in which the resin composition is used. The present invention provides a resin composition including a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and not including a radical polymerization initiator.
Description
\¥0 2020/175537 1 ?<:17 2020 /007686 \¥0 2020/175537 1 ?<:17 2020/007686
明 細 書 Specification
発明の名称 : Title of invention:
樹脂組成物、 プリプレグ、 金属箔張積層板、 樹脂複合シート、 および、 プ リント配線板 Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board
技術分野 Technical field
[0001 ] 本発明は、 樹脂組成物、 ならびに、 これを用いたプリプレグ、 金属箔張積 層板、 樹脂複合シート、 および、 プリント配線板に関する。 The present invention relates to a resin composition, a prepreg using the same, a metal foil laminated layer board, a resin composite sheet, and a printed wiring board.
背景技術 Background technology
[0002] 近年、 携帯端末をはじめ、 電子機器や通信機器等に用いられる半導体素子 の高集積化および微細化が加速している。 これに伴い、 半導体素子の高密度 実装を可能とする技術が求められており、 その重要な位置をしめるプリント 配線板についても改良が求められている。 [0002] In recent years, high integration and miniaturization of semiconductor elements used in electronic devices, communication devices and the like including mobile terminals have been accelerated. Along with this, technology that enables high-density mounting of semiconductor elements is required, and improvements are also required in printed wiring boards, which play an important role.
一方、 電子機器等の用途は多様化し拡大をつづけている。 これを受け、 プ リント配線板やこれに用いる金属箔張積層板、 プリプレグなどに求められる 諸特性も多様化し、 かつ厳しいものとなっている。 そうした要求特性を考慮 しながら、 改善されたプリント配線板を得るために、 各種の材料や加工法が 提案されている。 その 1つとして、 プリプレグを構成する樹脂材料の改良開 発が挙げられる。 On the other hand, the applications of electronic devices are diversifying and expanding. In response to this, various characteristics required for printed wiring boards, metal foil-clad laminates used for them, prepregs, etc. have become diversified and severe. Various materials and processing methods have been proposed in order to obtain improved printed wiring boards while taking such required characteristics into consideration. One of these is the development of resin materials that make up prepregs.
[0003] 例えば、 特許文献 1 には、 ポリフエニレンエーテル骨格を有する 2官能性 フエニレンエーテルオリゴマーの末端ビニル化合物 (3) 、 特定のマレイミ ド化合物 (13) 、 ナフトールアラルキル型のシアン酸エステル樹脂 (〇) お よびナフタレン骨格変性したノボラック型のエポキシ樹脂 (¢0 を含む樹脂 組成物が開示されている。 [0003] For example, Patent Document 1 discloses that a terminal vinyl compound (3) of a bifunctional phenylene ether oligomer having a polyphenylene ether skeleton, a specific maleimide compound (13), and a naphthol aralkyl type cyanate ester resin. A resin composition containing (O) and a novolac type epoxy resin (¢0) modified with a naphthalene skeleton is disclosed.
[0004] 特許文献 2では、 少なくとも一端にマレイミ ド基を有する樹脂 (1\1 , 1\1’ - 4 , 4’ ージフエニルメタンビスマレイミ ドとジアミンを原料とするアミ ノビスマレイミ ド系樹脂) と、 式 (〇 1) で示されるブロモ化スチレンと式 (〇 2) で示されるジビニルベンゼンとの共重合体とからなる難燃性樹脂組
〇 2020/175537 2020 /007686 [0004] In Patent Document 2, a resin having a maleimide group at least at one end (1\1, 1\1'-4, 4'-aminophenyl bismuthamide and an aminobismaleimide-based resin made of diamine as raw materials) And a flame-retardant resin group consisting of a brominated styrene represented by the formula (○ 1) and a copolymer of divinylbenzene represented by the formula (○ 2) 〇 2020/175 537 2020/007686
成物が開示されている。 A product is disclosed.
[化 1 ] [Chemical 1]
特許文献 Patent literature
[0005] 特許文献 1 :特開 2 0 1 〇- 1 3 8 3 6 4号公報 [0005] Patent Document 1: Japanese Unexamined Patent Publication No. 2 0 1 〇 -1 3 8 3 6 4
特許文献 2 :特開平 0 3 - 0 0 6 2 9 3号公報 Patent Document 2: Japanese Patent Laid-Open No. 03-060062993
発明の概要 Summary of the invention
発明が解決しようとする課題 Problems to be Solved by the Invention
[0006] 上述した例を含め、 その材料開発により、 プリント配線板における諸特性 の改良が進められてきているが、 技術の進展やアプリケーシヨンの拡大に鑑 みると、 さらなる性能の向上が求められる。 特に近年、 高い耐熱性を有しつ つ、 低誘電率 ·低誘電正接である材料が求められている。 [0006] The properties of printed wiring boards have been improved by developing the materials including the above-mentioned examples. However, further improvement in performance is required in view of technological progress and expansion of applications. .. In particular, in recent years, a material having a high heat resistance and a low dielectric constant/low dielectric loss tangent has been demanded.
本発明はかかる課題を解決することを目的とするものであって、 誘電率お よび誘電正接が低く、 耐熱性が高い樹脂組成物、 およびこれを用いたプリプ レグ、 金属箔張積層板、 樹脂複合シート、 プリント配線板の提供を目的とす る。 An object of the present invention is to solve such problems, and a resin composition having a low dielectric constant and a low dielectric loss tangent and high heat resistance, a prepreg using the same, a metal foil-clad laminate, and a resin. The purpose is to provide composite sheets and printed wiring boards.
課題を解決するための手段 Means for solving the problem
[0007] 上記課題のもと、 本発明者らはプリプレグ等のプリント配線板の用途に特 に適した樹脂組成物の成分組成を検討した結果、 多官能ビニル芳香族重合体 と熱硬化性化合物とを組み合わせた樹脂組成物は、 低誘電率 ·低誘電正接を 示し、 かつ、 耐熱性が高いことが分かった。 しかしながら、 ラジカル重合開 始剤を添加すると、 これらの性能が劣ることが分かった。 本発明はかかる知
〇 2020/175537 3 卩(:171? 2020 /007686 Under the above problems, the present inventors have investigated the component composition of a resin composition that is particularly suitable for the use of printed wiring boards such as prepregs. As a result, the polyfunctional vinyl aromatic polymer and thermosetting compound have been obtained. It was found that the resin composition in which the combination of and showed a low dielectric constant and a low dielectric loss tangent and high heat resistance. However, it was found that these properties were inferior when a radical polymerization initiator was added. The present invention is 〇 2020/175 537 3 卩 (:171? 2020 /007686
見により完成されるに至ったものであり、 具体的には、 下記手段<1>によ り、 好ましくは<2>〜<1 1>により、 上記課題は解決された。 The above problems have been solved by the following means <1>, preferably <2> to <11>.
[0008] <1>多官能ビニル芳香族重合体 ( ) と熱硬化性化合物 (巳) とを含み、 ラジカル重合開始剤を含まない樹脂組成物。 <1> A resin composition containing a polyfunctional vinyl aromatic polymer () and a thermosetting compound (M), and containing no radical polymerization initiator.
< 2>前記多官能ビニル芳香族重合体 ( ) が、 式 (V) で表される構成単 位を有する重合体である、 < 1>に記載の樹脂組成物。 <2> The resin composition according to <1>, wherein the polyfunctional vinyl aromatic polymer () is a polymer having a structural unit represented by the formula (V).
[化 2] [Chemical 2]
(式中、 「は芳香族炭化水素連結基を表す。 *は、 結合位置を表す。 ) <3>前記熱硬化性化合物 (巳) がシアナト基、 ビニル基、 マレイミ ド基、 およびナジイミ ド基からなる群より選ばれる 1つ以上の官能基を有する、 < 1>または<2>に記載の樹脂組成物。 (In the formula, "represents an aromatic hydrocarbon linking group. * represents a bonding position.) <3> The thermosetting compound (M) is a cyanato group, a vinyl group, a maleimide group, and a nadiimide group. The resin composition according to <1> or <2>, which has one or more functional groups selected from the group consisting of:
<4>樹脂組成物中の樹脂成分の総量 1 0 0質量部に対する、 前記熱硬化性 化合物 (巳) の含有量が、 5〜 9 5質量部である、 <1>〜<3>のいずれ か 1つに記載の樹脂組成物。 <4> Any one of <1> to <3>, in which the content of the thermosetting compound (Mitsumi) is 5 to 95 parts by mass with respect to 100 parts by mass of the total amount of resin components in the resin composition. The resin composition according to 1 above.
< 5>樹脂組成物中の樹脂成分の総量 1 0 0質量部に対する、 前記多官能ビ ニル芳香族重合体 ( ) の含有量が、 5〜 9 5質量部である、 <1>〜<4 >のいずれか 1つに記載の樹脂組成物。 <5> The content of the polyfunctional vinyl aromatic polymer () is 5 to 95 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition, <1> to <4. > The resin composition of any one of.
< 6>さらに充填材 (〇 を含む、 < 1>〜<5>のいずれか 1つに記載の 樹脂組成物。 <6> The resin composition according to any one of <1> to <5>, further including a filler (○).
< 7>樹脂組成物中の樹脂成分の総量 1 0 0質量部に対する、 前記充填材 ( 〇) の含有量が、 1 〇〜 5 0 0質量部である、 <6>に記載の樹脂組成物。 <8>基材と、 <1>〜<7>のいずれか 1つに記載の樹脂組成物とから形 成された、 プリプレグ。 <7> The resin composition according to <6>, in which the content of the filler (◯) is 100 to 500 parts by mass with respect to 100 parts by mass of the total amount of resin components in the resin composition. .. A prepreg formed from a <8> substrate and the resin composition according to any one of <1> to <7>.
< 9><8>に記載のプリプレグから形成された少なくとも 1つの層と、 前
〇 2020/175537 4 卩(:171? 2020 /007686 <9> at least one layer formed from the prepreg according to <8>, and 〇 2020/175 537 4 卩 (:171? 2020 /007686
記プリプレグから形成された層の片面または両面に配置された金属箔とを含 む、 金属箔張積層板。 A metal foil-clad laminate comprising a layer formed from the prepreg and a metal foil disposed on one side or both sides of the layer.
<1 〇>支持体と、 前記支持体の表面に配置された<1>〜< 7>のいずれ か 1つに記載の樹脂組成物から形成された層とを含む、 樹脂複合シート。 <1 1>絶縁層と、 前記絶縁層の表面に配置された導体層とを含むプリント 配線板であって、 前記絶縁層が、 < 1>〜<7>のいずれか 1つに記載の樹 脂組成物から形成された層および< 8>に記載のプリプレグから形成された 層の少なくとも一方を含む、 プリント配線板。 <10> A resin composite sheet comprising a support and a layer formed on the surface of the support and formed from the resin composition according to any one of <1> to <7>. <11> A printed wiring board comprising an insulating layer and a conductor layer arranged on the surface of the insulating layer, wherein the insulating layer is any one of <1> to <7>. A printed wiring board comprising at least one of a layer formed from a resin composition and a layer formed from the prepreg according to <8>.
発明の効果 Effect of the invention
[0009] 本発明により、 誘電率および誘電正接が低く、 耐熱性が高い樹脂組成物、 およびこれを用いたプリプレグ、 金属箔張積層板、 樹脂複合シート、 プリン 卜配線板を提供可能になった。 According to the present invention, it is possible to provide a resin composition having a low dielectric constant and dielectric loss tangent and high heat resistance, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the same. ..
発明を実施するための形態 MODE FOR CARRYING OUT THE INVENTION
[0010] 以下において、 本発明の内容をその好ましい実施形態に沿って詳細に説明 する。 なお、 本明細書において 「〜」 とはその前後に記載される数値を下限 値および上限値として含む意味で使用される。 [0010] In the following, the content of the present invention will be described in detail along with its preferred embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.
[001 1 ] 本実施形態に係る樹脂組成物は、 多官能ビニル芳香族重合体 ( ) と熱硬 化性化合物 (巳) とを含み、 ラジカル重合開始剤を含まないことを特徴とす る。 [001 1] The resin composition according to the present embodiment is characterized by containing a polyfunctional vinyl aromatic polymer () and a thermosetting compound (M) and not containing a radical polymerization initiator.
このような構成とすることにより、 誘電率および誘電正接が低く、 耐熱性 が高い樹脂組成物を提供可能になる。 さらに、 ピール強度を高くすることも 可能になる。 また、 その他の各種性能も向上させることが可能になる。 特に 近年、 通信や動作信号が高周波数化する傾向にあるが、 本実施形態に係る樹 脂組成物は、 高周波数領域でも、 低誘電率 ·低誘電正接を達成し、 耐熱性を 高くすることが可能である。 With such a structure, it is possible to provide a resin composition having a low dielectric constant and a low dielectric loss tangent and high heat resistance. Furthermore, it is possible to increase the peel strength. It is also possible to improve various other performances. Especially in recent years, there is a tendency for communication and operation signals to have high frequencies, but the resin composition according to the present embodiment achieves low dielectric constant and low dielectric loss tangent and high heat resistance even in a high frequency region. Is possible.
この理由は、 以下に限定されないが、 以下のとおりであると考えられる。 すなわち、 本実施形態に係る樹脂組成物は、 多官能ビニル芳香族重合体 (八 ) や熱硬化性化合物 (巳) が有する熱硬化性基が熱によって硬化する熱硬化
〇 2020/175537 5 卩(:171? 2020 /007686 The reason for this is not limited to the following, but is considered to be as follows. That is, the resin composition according to this embodiment is a thermosetting resin in which the thermosetting group of the polyfunctional vinyl aromatic polymer (8) or the thermosetting compound (M) is cured by heat. 〇 2020/175 537 5 卩 (:171? 2020 /007686
性樹脂組成物である。 このような樹脂組成物が熱ラジカル重合開始剤を含ま ない場合、 多官能ビニル芳香族重合体 ( ) の重合開始温度と熱硬化性化合 物 (巳) の重合開始温度とが近くなり、 多官能ビニル芳香族重合体 ( ) と 熱硬化性化合物 (巳) が共に十分に硬化でき、 その結果、 低誘電率 ·低誘電 正接、 高耐熱性を達成できると考えられる。 また、 光ラジカル重合開始剤を 含まないことにより、 保存時に遮光をしなくても、 多官能ビニル芳香族重合 体 ( ) や熱硬化性化合物 (巳) の光硬化を効果的に抑制できる。 Resin composition. When such a resin composition does not contain a thermal radical polymerization initiator, the polymerization initiation temperature of the polyfunctional vinyl aromatic polymer () and the polymerization initiation temperature of the thermosetting compound (M) are close to each other, and It is considered that the vinyl aromatic polymer () and the thermosetting compound (M) can be sufficiently cured, and as a result, low dielectric constant, low dielectric loss tangent, and high heat resistance can be achieved. Further, by not containing the photo-radical polymerization initiator, the photo-curing of the polyfunctional vinyl aromatic polymer () and the thermosetting compound (M) can be effectively suppressed without shading during storage.
なお、 本実施形態に係る樹脂組成物は、 光によって硬化を進行させるので はなく、 主に、 熱によって硬化を進行させる非感光性熱硬化性樹脂組成物で あることが好ましい。 The resin composition according to the present embodiment is preferably a non-photosensitive thermosetting resin composition that is not cured by light but is cured mainly by heat.
[0012] <多官能ビニル芳香族重合体 (八) > [0012] <Polyfunctional vinyl aromatic polymer (8)>
本実施形態に係る樹脂組成物は、 多官能ビニル芳香族重合体 ( ) を含有 する。 The resin composition according to the present embodiment contains a polyfunctional vinyl aromatic polymer ().
多官能ビニル芳香族重合体 (八) は、 2つ以上のビニル基を分子内に有す る芳香族化合物を重合させた重合体であることが好ましい。 2つ以上のビニ ル基を分子内に有する芳香族化合物は、 例えば、 ビニル基について、 各位置 異性体のいずれであってもよく、 また、 そのような位置異性体の混合物であ ってもよい。 より具体的には、 多官能ビニル芳香族重合体 (八) が 2つのビ ニル基を分子内に有する芳香族化合物である場合、
体、 〇—体 またはこれらの位置異性体混合物のいずれであってもよく、
体 またはこれらの位置異性体混合物のいずれかであることが好ましい。 The polyfunctional vinyl aromatic polymer (8) is preferably a polymer obtained by polymerizing an aromatic compound having two or more vinyl groups in the molecule. The aromatic compound having two or more vinyl groups in the molecule may be, for example, any of the positional isomers of a vinyl group, or may be a mixture of such positional isomers. Good. More specifically, when the polyfunctional vinyl aromatic polymer (8) is an aromatic compound having two vinyl groups in the molecule, Body, O-body or a mixture of these positional isomers, It is preferably either the body or a mixture of these positional isomers.
多官能ビニル芳香族重合体 ( ) を構成する単量体としては、 1つまたは 2つ以上のビニル基を有する芳香族化合物 (以下、 2つ以上のビニル基を有 する芳香族化合物を多官能ビニル芳香族化合物ともいう) が挙げられ、 1つ または 2つのビニル基を有する芳香族化合物であることが好ましい。 例えば 、 多官能ビニル芳香族重合体 ( ) として、 2つのビニル基を有する芳香族 化合物 (ジビニル芳香族化合物ともいう) に由来する構成単位 (3) と、 1 つのビニル基を有する芳香族化合物に由来する構成単位 (匕) を含む重合体
〇 2020/175537 6 卩(:171? 2020 /007686 As a monomer constituting the polyfunctional vinyl aromatic polymer (), an aromatic compound having one or more vinyl groups (hereinafter, an aromatic compound having two or more vinyl groups is (Also referred to as a vinyl aromatic compound), and an aromatic compound having one or two vinyl groups is preferable. For example, as a polyfunctional vinyl aromatic polymer (), a structural unit (3) derived from an aromatic compound having two vinyl groups (also referred to as a divinyl aromatic compound) and an aromatic compound having one vinyl group Polymers containing derived structural units 〇 2020/175 537 6 卩 (:171? 2020 /007686
が例示される。 Is exemplified.
[0013] 構成単位 (3) を形成するジビニル芳香族化合物は、 炭化水素芳香族環を 有する化合物であることが好ましく、 ジビニルベンゼン、 ジアリルベンゼン 、 ビス (ビニルオキシ) ベンゼン、 ビス (1 —メチルビニル) ベンゼン、 ジ ビニルナフタレン、 ジビニルアントラセン、 ジビニルビフエニル、 ジビニル フエナントレン、 ビス (4—アリルオキシフエニル) フルオレンなどが挙げ られる。 中でもジビニルベンゼンが特に好ましい。 ジビニル芳香族化合物に 由来する構成単位の重合体中での形態は、 (3 _ 1) ビニル基の 1つだけが 重合反応し、 もう 1つのビニル基が未反応のまま残された形態と、 (3— 2 ) 2つとも重合反応した形態とがあり得る。 本実施形態においては、 ビニル 基の一方が反応せずに残された形態 ( 3 _ 1) が含まれることが好ましい。 なお、 多官能ビニル芳香族化合物 (好ましくはジビニル芳香族化合物) は、 本発明の効果を奏する範囲で任意の置換基 (例えば、 炭素数 1〜 6のアル キル基、 炭素数 2〜 6のアルケニル基、 炭素数 2〜 6のアルキニル基、 炭素 数 1〜 6のアルコキシ基、 ヒドロキシ基、 アミノ基、 カルボキシ基、 ハロゲ ン原子等が挙げられる) を有していてもよい。 The divinylaromatic compound forming the structural unit (3) is preferably a compound having a hydrocarbon aromatic ring, such as divinylbenzene, diallylbenzene, bis(vinyloxy)benzene, bis(1-methylvinyl). Examples thereof include benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene and bis(4-allyloxyphenyl)fluorene. Of these, divinylbenzene is particularly preferable. The morphology in the polymer of the constitutional unit derived from the divinyl aromatic compound is such that only one of the (3 _ 1) vinyl groups undergoes a polymerization reaction and the other vinyl group remains unreacted. (3-2) Both may have a form in which they are polymerized. In the present embodiment, it is preferable to include a form (3 — 1) in which one of the vinyl groups is left unreacted. The polyfunctional vinyl aromatic compound (preferably divinyl aromatic compound) is an arbitrary substituent (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms) within the range that the effect of the present invention is exhibited. Group, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, an amino group, a carboxy group, a halogen atom, and the like).
[0014] 上記の多官能ビニル芳香族化合物 (好ましくはジビニル芳香族化合物) に 由来する構成単位 (3) は、 下記式 (V) で表される構成単位を含むことが 好ましい。 The structural unit (3) derived from the above polyfunctional vinyl aromatic compound (preferably divinyl aromatic compound) preferably contains a structural unit represented by the following formula (V).
[化 3] [Chemical 3]
式 (V) 中、 「は芳香族炭化水素連結基を表す。 具体例としては、 下記 1_ 1の例が挙げられる。 式中の氺は結合位置を表す。 In Formula (V), at "as the. Specific examples of an aromatic hydrocarbon linking group, the氺in. Formula which is, for example, the following 1_ 1 represents a bonding position.
芳香族炭化水素連結基とは、 置換基を有していてもよい芳香族炭化水素の みからなる基であってもよいし、 置換基を有していてもよい芳香族炭化水素
〇 2020/175537 7 卩(:171? 2020 /007686 The aromatic hydrocarbon linking group may be a group consisting of only an aromatic hydrocarbon that may have a substituent, or an aromatic hydrocarbon that may have a substituent. 〇 2020/175 537 7 (:171? 2020/007686
と他の連結基の組み合わせからなる基であってもよく、 置換基を有していて もよい芳香族炭化水素のみからなる基であることが好ましい。 なお、 芳香族 炭化水素が有していてもよい置換基は、 上述の置換基 が挙げられる。 また 、 上記芳香族炭化水素は、 置換基を有さない方が好ましい。 And a group consisting of other linking groups, and preferably a group consisting only of an aromatic hydrocarbon which may have a substituent. The substituents that the aromatic hydrocarbon may have include the above-mentioned substituents. Further, it is preferable that the aromatic hydrocarbon does not have a substituent.
芳香族炭化水素連結基は、 通常、 2価の連結基である。 The aromatic hydrocarbon linking group is usually a divalent linking group.
[0015] 芳香族炭化水素連結基は、 具体的には、 置換基を有していてもよい、 フエ ニレン基、 ナフタレンジイル基、 アントラセンジイル基、 フエナントレンジ イル基、 ビフエニルジイル基、 フルオレンジイル基が挙げられ、 中でも置換 基を有していてもよいフエニレン基が好ましい。 置換基は、 上述の置換基 が例示されるが、 上述したフエニレン基等の基は置換基を有さない方が好ま しい。 [0015] Specific examples of the aromatic hydrocarbon linking group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group and a fluorenediyl group which may have a substituent. And a phenylene group which may have a substituent is preferable. Examples of the substituent include the above-mentioned substituents, but it is preferable that the above-mentioned groups such as the phenylene group do not have a substituent.
[0016] 多官能ビニル芳香族化合物 (好ましくはジビニル芳香族化合物) に由来す る構成単位 (3) は、 下記式 (V I) で表される構成単位、 下記式 (V 2) で表される構成単位、 および下記式 い/ 3) で表される構成単位の少なくと も 1つを含むことがより好ましい。 なお、 下記式中の*は結合位置を表す。 A structural unit (3) derived from a polyfunctional vinyl aromatic compound (preferably a divinyl aromatic compound) is a structural unit represented by the following formula (VI) and a structural unit represented by the following formula (V 2) It is more preferable to include a structural unit and at least one structural unit represented by the following formula (3): In addition, * in the following formula represents a bonding position.
[0017] [化 4] [0017] [Chemical 4]
式 (V I) 〜 ( 3) 中、 1_ 1は芳香族炭化水素連結基 (炭素数 6〜 2 2が 好ましく、 6〜 1 8がより好ましく、 6〜 1 0がさらに好ましい) である。 具体的には、 置換基を有していてもよい、 フエニレン基、 ナフタレンジイル 基、 アントラセンジイル基、 フエナントレンジイル基、 ビフエニルジイル基 、 フルオレンジイル基が挙げられ、 中でも置換基を有していてもよいフエニ レン基が好ましい。 置換基は、 上述の置換基 が例示されるが、 上述したフ エニレン基等の基は置換基を有さない方が好ましい。
〇 2020/175537 8 卩(:171? 2020 /007686 Wherein (VI) ~ (3), 1_ 1 is an aromatic hydrocarbon linking group (preferably the number of 6 to 2 2 carbon atoms, 6 to more preferably 1 8, more preferably 6 to 1 0). Specific examples thereof include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may have a substituent. Preferred are phenylene groups. Examples of the substituent include the above-mentioned substituents, but the above-mentioned groups such as a phenylene group preferably have no substituent. 〇 2020/175 537 8 卩 (:171? 2020 /007686
[0018] 多官能ビニル芳香族重合体 ( ) は、 上述のとおり、 構成単位 (3) の単 独重合体であってもよいが、 構成単位 (匕) 等との共重合体であってもよい 。 多官能ビニル芳香族重合体 ( ) は、 共重合体であるとき、 その共重合比 は、 構成単位 ( 3) が 5モル%以上であることが好ましく、 1 0モル%以上 であることがより好ましく、 1 5モル%以上であることがさらに好ましい。 上限値としては、 9 0モル%以下であることが実際的である。 [0018] The polyfunctional vinyl aromatic polymer () may be a homopolymer of the structural unit (3) as described above, or may be a copolymer with the structural unit (digest) or the like. Good. When the polyfunctional vinyl aromatic polymer () is a copolymer, the copolymerization ratio of the structural unit (3) is preferably 5 mol% or more, and more preferably 10 mol% or more. It is more preferably 15 mol% or more. The upper limit is practically 90 mol% or less.
[0019] 多官能ビニル芳香族重合体 ( ) が、 モノビニル芳香族化合物に由来する 構成単位 (匕) を含む共重合体であるとき、 モノビニル芳香族化合物の例と しては、 スチレン、 ビニルナフタレン、 ビニルビフエニルなどのビニル芳香 族化合物; 〇-メチルスチレン、 ーメチルスチレン、 ーメチルスチレン 、 〇,
ジメチルスチレン、 〇—エチルビニルベンゼン、 01—エチルビニ ルベンゼン、 _エチルビニルベンゼン、 メチルビニルビフエニル、 エチル ビニルビフエニルなどの核アルキル置換ビニル芳香族化合物などが挙げられ る。 ここで例示したモノビニル芳香族化合物は適宜上述の置換基 を有して いてもよい。 また、 これらのモノビニル芳香族化合物は、 1種を用いても 2 種以上を用いてもよい。 [0019] When the polyfunctional vinyl aromatic polymer () is a copolymer containing a structural unit (shallow) derived from a monovinyl aromatic compound, examples of the monovinyl aromatic compound include styrene and vinylnaphthalene. , Vinyl aromatic compounds such as vinylbiphenyl; 〇-methylstyrene, -methylstyrene, -methylstyrene, 〇, Nuclear alkyl-substituted vinyl aromatic compounds such as dimethylstyrene, O-ethylvinylbenzene, 01-ethylvinylbenzene, _ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl are listed. The monovinyl aromatic compounds exemplified here may optionally have the above-mentioned substituents. These monovinyl aromatic compounds may be used alone or in combination of two or more.
[0020] モノビニル芳香族化合物に由来する構成単位 (匕) は、 下記式 ( 4) で 表される構成単位であることが好ましい。 [0020] The constitutional unit derived from the monovinyl aromatic compound (the bowl) is preferably a constitutional unit represented by the following formula (4).
[0021 ] [化 5] [0021] [Chemical 5]
式 ( 4) 中、 !_ 2は芳香族炭化水素連結基であり、 好ましいものの具体例 としては、 上記 !_ 1の例が挙げられる。 Formula (4) Medium,! _ 2 is an aromatic hydrocarbon linking group, and specific examples of preferable ones include the examples of !_ 1 above.
は水素原子または炭素数 1〜 1 2の炭化水素基 (好ましくはアルキル 基) である。
が炭化水素基であるとき、 その炭素数は 1〜 6が好ましく 、 1〜 3がより好ましい。 および 1_ 2は上述の置換基 を有していてもよ
〇 2020/175537 9 卩(:171? 2020 /007686 Is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). Is a hydrocarbon group, its carbon number is preferably 1 to 6, and more preferably 1 to 3. And 1_ 2 have the above substituent 〇 2020/175 537 9 卩 (:171? 2020 /007686
い。 Yes.
[0022] 多官能ビニル芳香族重合体 ( ) が構成単位 (匕) を含む共重合体である とき、 構成単位 (匕) の共重合比は、 1 0モル%以上であることが好ましく 、 1 5モル%以上であることがさらに好ましい。 上限値としては、 9 8モル %以下であることが好ましく、 9 0モル%以下であることがより好ましく、 [0022] When the polyfunctional vinyl aromatic polymer () is a copolymer containing a structural unit (shallow), the copolymerization ratio of the structural unit (shallow) is preferably 10 mol% or more, 1 It is more preferably at least 5 mol %. The upper limit is preferably 98 mol% or less, more preferably 90 mol% or less,
8 5モル%以下であることがさらに好ましい。 It is more preferably 85 mol% or less.
[0023] 多官能ビニル芳香族重合体 ( ) は、 その他の構成単位を有していてもよ い。 その他の構成単位としては、 例えば、 シクロオレフィン化合物に由来す る構成単位 (〇) などが挙げられる。 シクロオレフィン化合物としては、 環 構造内に二重結合を有する炭化水素類が挙げられる。 具体的に、 シクロブテ ン、 シクロペンテン、 シクロヘキセン、 シクロオクテンなどの単環の環状才 レフインの他、 ノルボルネン、 ジシクロペンタジェンなどのノルボルネン環 構造を有する化合物、 インデン、 アセナフチレンなどの芳香族環が縮合した シクロオレフィン化合物などを挙げることができる。 ノルボルネン化合物の 例としては、 特開 2 0 1 8 - 3 9 9 9 5号公報の段落 0 0 3 7〜〇 0 4 3に 記載のものが挙げられ、 これの内容は本明細書に組み込まれる。 なお、 ここ で例示したシクロオレフィン化合物はさらに上述の置換基 を有していても よい。 [0023] The polyfunctional vinyl aromatic polymer () may have other structural units. Examples of the other structural unit include a structural unit (◯) derived from a cycloolefin compound. Examples of the cycloolefin compound include hydrocarbons having a double bond in the ring structure. Specifically, in addition to monocyclic cyclic refynes such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, compounds having a norbornene ring structure such as norbornene and dicyclopentagen, and aromatic rings such as indene and acenaphthylene were condensed. A cycloolefin compound etc. can be mentioned. Examples of norbornene compounds include those described in paragraphs 0 0 3 7 to 0 0 4 3 of JP-A No. 2018-39995, the contents of which are incorporated herein. .. The cycloolefin compounds exemplified here may further have the above-mentioned substituents.
[0024] 多官能ビニル芳香族重合体 ( ) が構成単位 (〇) を含む共重合体である とき、 構成単位 (〇) の共重合比は、 1 0モル%以上であることが好ましく 、 2 0モル%以上であることがより好ましく、 3 0モル%以上であることが さらに好ましい。 上限値としては、 9 0モル%以下であることが好ましく、 [0024] When the polyfunctional vinyl aromatic polymer () is a copolymer containing the structural unit (○), the copolymerization ratio of the structural unit (○) is preferably 10 mol% or more, 2 It is more preferably 0 mol% or more, and further preferably 30 mol% or more. The upper limit is preferably 90 mol% or less,
8 0モル%以下であることがより好ましく、 7 0モル%以下であることがさ らに好ましく、 5 0モル%以下であってもよく、 3 0モル%以下であっても よい。 It is more preferably 80 mol% or less, further preferably 70 mol% or less, 50 mol% or less, or 30 mol% or less.
[0025] 多官能ビニル芳香族重合体 (八) にはさらに異なる重合性化合物 (以下、 他の重合性化合物ともいう) に由来する構成単位 (〇1) が組み込まれていて もよい。 他の重合性化合物 (単量体) としては、 例えば、 ビニル基を 3つ含
〇 2020/175537 10 卩(:171? 2020 /007686 [0025] The polyfunctional vinyl aromatic polymer (8) may further incorporate a structural unit (O1) derived from a different polymerizable compound (hereinafter, also referred to as other polymerizable compound). Other polymerizable compounds (monomers) include, for example, 3 vinyl groups. 〇 2020/175 537 10 卩 (:171? 2020 /007686
む化合物が挙げられる。 具体的には、 1 , 3 , 5 -トリビニルベンゼン、 1 , 3 , 5—トリビニルナフタレン、 1 , 2 , 4—トリビニルシクロヘキサン が挙げられる。 あるいは、 エチレングリコールジアクリレート、 ブタジエン 等が挙げられる。 他の重合性化合物に由来する構成単位 (¢0 の共重合比は 、 3 0モル%以下であることが好ましく、 2 0モル%以下であることがより 好ましく、 1 0モル%以下であることがさらに好ましい。 Compounds. Specific examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene and 1,2,4-trivinylcyclohexane. Alternatively, ethylene glycol diacrylate, butadiene, etc. may be mentioned. A structural unit derived from another polymerizable compound (copolymerization ratio of 0 is preferably 30 mol% or less, more preferably 20 mol% or less, and 10 mol% or less. Is more preferable.
[0026] 多官能ビニル芳香族重合体 ( ) の一実施形態として、 構成単位 (3) を 必須とし、 構成単位 (匕) 〜 (¢0 の少なくとも 1種を含む重合体が例示さ れる。 さらには、 構成単位 (3) 〜 (¢0 の合計が、 全構成単位の 9 5モル %以上、 さらには 9 8モル%以上を占める態様が例示される。 [0026] As one embodiment of the polyfunctional vinyl aromatic polymer (), a polymer including the structural unit (3) as an essential component and including at least one of the structural units (distance) to (¢0) is exemplified. Is exemplified by an embodiment in which the total of the structural units (3) to (0) accounts for 95 mol% or more, and more preferably 98 mol% or more of all the structural units.
多官能ビニル芳香族重合体 ( ) の他の _実施形態として、 構成単位 (3 ) を必須とし、 末端を除く全構成単位のうち、 芳香族環を含む構成単位が 9 0モル%以上のものであることが好ましく、 9 5モル%以上のものであるこ とがより好ましく、 1 0 0モル%のものであってもよい。 As another __ embodiment of the polyfunctional vinyl aromatic polymer (), the constitutional unit (3) is essential, and the constitutional unit containing an aromatic ring is 90 mol% or more of all constitutional units excluding the end. Is preferable, more preferably 95 mol% or more, and even more preferably 100 mol%.
全構成単位当たりのモル%を算出するにあたり、 1つ構成単位とは、 多官 能ビニル芳香族重合体 ( ) を構成する単量体 1分子に由来するものとする In calculating the mol% per all structural units, one structural unit shall be derived from one molecule of the monomer that constitutes the multi-functional vinyl aromatic polymer ().
[0027] 多官能ビニル芳香族重合体 (八) の製造方法は特に限定されず常法によれ ばよいが、 例えば、 ジビニル芳香族化合物を含むモノマーを (必要により、 モノビニル芳香族化合物、 シクロオレフイン化合物等を共存させ) 、 ルイス 酸触媒の存在下で重合させることが挙げられる。 ルイス酸触媒としては、 金 属フッ化物またはその錯体を用いることができる。 [0027] The method for producing the polyfunctional vinyl aromatic polymer (8) is not particularly limited and may be a conventional method. For example, a monomer containing a divinyl aromatic compound (if necessary, a monovinyl aromatic compound, cycloolefin) may be used. Compounds and the like), and polymerizing in the presence of a Lewis acid catalyst. As the Lewis acid catalyst, metal fluoride or its complex can be used.
[0028] 多官能ビニル芳香族重合体 ( ) の鎖末端の構造は特に限定されないが、 上記ジビニル芳香族化合物に由来する基について言うと、 以下の式 (巳 1) の構造を取ることが挙げられる。 なお、 式 (巳 1) 中の は上記式 (V I) で規定したものと同じである。 氺は結合位置を表す。 [0028] The structure of the chain end of the polyfunctional vinyl aromatic polymer () is not particularly limited, but the group derived from the above divinyl aromatic compound is exemplified by the structure of the following formula (M1). To be Note that in (Equation 1) is the same as that defined in the above equation (VI). The symbol represents the bonding position.
氺一〇 1~1 =〇 1~1 - 1_ 1 -〇 1~1 =〇 1~1 2 (巳 1) 氺ten 1 to 1 = 〇 1 to 1 - 1_ 1 -〇 1 to 1 = 〇 1 to 1 2 (only 1)
[0029] モノビニル芳香族化合物に由来する基が鎖末端となったときには、 下記式
〇 2020/175537 11 卩(:171? 2020 /007686 [0029] When the group derived from the monovinyl aromatic compound becomes a chain end, 〇 2020/175537 11 卩(: 171-1?2020/007686
(巳 2) の構造を取ることが挙げられる。 式中の!-2および VIはそれぞれ前 記の式 ( 4) で定義したものと同じ意味である。 *は結合位置を表す。 One example is the structure of (Mimi 2). In the ceremony! - 2 and VI are the same meaning as defined in formula (4) before SL, respectively. * Represents a bonding position.
氺一〇 1~1 =〇 1~1 - 1_ 2- 1 (巳 2) 氺ten 1 to 1 = 〇 1 to 1 - 1 _ 2 - 1 (only 2)
[0030] 多官能ビニル芳香族重合体 (八) の分子量は、 数平均分子量 IV! nで、 30 [0030] The polyfunctional vinyl aromatic polymer (8) has a number average molecular weight IV! n of 30
0以上であることが好ましく、 500以上であることがより好ましく、 1 , It is preferably 0 or more, more preferably 500 or more, 1,
000以上であることがさらに好ましい。 上限としては、 1 00, 000以 下であることが好ましく、 1 0, 000以下であることがより好ましく、 5 , 000以下であることがさらに好ましく、 4, 000以下であることがさ らに好ましい。 重量平均分子量 IV! と数平均分子量 IV! nの比で表される単分 散度 (Mw/Mn) は、 1 00以下であることが好ましく、 50以下である ことがより好ましく、 20以下であることがさらに好ましい。 下限値として は、 1. 1以上であることが実際的である。 多官能ビニル芳香族重合体 (八 ) は、 トルエン、 キシレン、 テトラヒドロフラン、 ジクロロエタンまたはク ロロホルムに可溶であることが好ましい。 More preferably, it is 000 or more. The upper limit is preferably 100,000 or less, more preferably 100,000 or less, further preferably 5,000 or less, and further preferably 4,000 or less. preferable. The monodispersity (Mw/Mn) represented by the ratio of the weight average molecular weight IV! and the number average molecular weight IV! n is preferably 100 or less, more preferably 50 or less, and more preferably 20 or less. It is more preferable that there is. It is practical that the lower limit value is 1.1 or more. The polyfunctional vinyl aromatic polymer (8) is preferably soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.
[0031] 本明細書において多官能ビニル芳香族重合体 ( ) については、 国際公開 第 201 7/1 1 581 3号の段落 0029〜〇 058に記載の化合物およ びその合成反応条件等、 特開 201 8 _ 039995号公報の段落 001 3 〜 0058に記載の化合物およびその合成反応条件等、 特開 201 8_ 1 6 8347号公報の段落 0008〜 0043に記載の化合物およびその合成反 応条件等、 特開 2006— 0701 36号公報の段落 001 4〜〇 042に 記載の化合物およびその合成反応条件等、 特開 2006 _ 089683号公 報の段落〇 01 4〜 006 1 に記載の化合物およびその合成反応条件等、 特 開 2008— 248001号公報の段落 0008〜〇 036に記載の化合物 およびその合成反応条件等を参照することができ、 本明細書に組み込まれる In the present specification, the polyfunctional vinyl aromatic polymer () is described in the compounds described in paragraphs 0029 to 〇 058 of International Publication No. 2017/1 1 5813, the synthesis reaction conditions thereof, and the like. Compounds described in paragraphs 001 3 to 0058 of JP 2018_039995 and synthesis reaction conditions thereof, and the like, compounds described in paragraphs 0008 to 0043 of JP 2018_16 8347 and synthesis reaction conditions thereof, etc. The compounds described in paragraphs 001 4 to 〇 042 of Kai 2006-0701 36 and the synthesis reaction conditions thereof, etc., and the compounds described in paragraphs 〇 01 4 to 006 1 of JP 2006_089683 publication and the synthesis reaction conditions thereof Etc., the compounds described in paragraphs 0008 to 036 of Japanese Patent Publication No. 2008-248001 and the synthesis reaction conditions thereof, etc. can be referred to and incorporated into the present specification.
[0032] 多官能ビニル芳香族重合体 ( ) の含有量は、 樹脂組成物中の樹脂成分の 総量を 1 00質量部としたとき、 5質量部以上であることが好ましく、 1 0 質量部以上であることがより好ましく、 1 5質量部以上であることがさらに
〇 2020/175537 12 卩(:171? 2020 /007686 [0032] The content of the polyfunctional vinyl aromatic polymer () is preferably 5 parts by mass or more, and 10 parts by mass or more, when the total amount of the resin components in the resin composition is 100 parts by mass. It is more preferable that the amount is 15 parts by mass or more. 〇 2020/175 537 12 卩 (:171? 2020 /007686
好ましく、 2 0質量部以上であることが一層好ましく、 さらには、 3 0質量 部以上、 4 0質量部以上、 5 0質量部以上、 6 0質量部以上であってもよい 。 多官能ビニル芳香族重合体 ( ) の含有量を上記の下限値以上とすること で、 特に、 低誘電率を効果的に達成できる。 他方、 多官能ビニル芳香族重合 体 ( ) の含有量の上限値は、 樹脂組成物中の樹脂成分の総量を 1 0 0質量 部としたとき、 9 5質量部以下であることが好ましく、 9 0質量部以下であ ることがより好ましく、 8 5質量部以下であることがさらに好ましく、 8 0 質量部以下であることが一層好ましい。 The amount is more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, and 60 parts by mass or more. By setting the content of the polyfunctional vinyl aromatic polymer () to be the above lower limit value or more, particularly low dielectric constant can be effectively achieved. On the other hand, the upper limit of the content of the polyfunctional vinyl aromatic polymer () is preferably 95 parts by mass or less when the total amount of the resin components in the resin composition is 100 parts by mass. It is more preferably 0 parts by mass or less, further preferably 85 parts by mass or less, and further preferably 80 parts by mass or less.
多官能ビニル芳香族重合体 ( ) は、 樹脂組成物中に、 1種のみ含まれて いても、 2種以上含まれていてもよい。 2種以上含まれる場合は、 合計量が 上記範囲となることが好ましい。 The polyfunctional vinyl aromatic polymer () may be contained in the resin composition in only one kind or in two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.
なお、 樹脂成分とは、 多官能ビニル芳香族重合体 (八) および熱硬化性化 合物 (巳) 並びに後述する他の樹脂を含む。 The resin component includes a polyfunctional vinyl aromatic polymer (8), a thermosetting compound (M), and other resins described later.
[0033] <熱硬化性化合物 (巳) > <Thermosetting Compound (Mimi)>
本実施形態に係る樹脂組成物は、 熱硬化性化合物 (巳) を含有する。 本明 細書において熱硬化性化合物 (巳) とは、 多官能ビニル芳香族重合体 (八) 以外の熱硬化性化合物を意味する。 熱硬化性化合物 (巳) としては、 シアナ 卜基、 ビニル基 (ただし、 多官能ビニル芳香族重合体となる基、 マレイミ ド 基、 ナジイミ ド基は含まない。 ビニルフエニル基が好ましい。 ) 、 マレイミ ド基、 およびナジイミ ド基からなる群より選ばれる 1つ以上の官能基を有す る化合物が好ましく、 シアナト基を有するシアン酸エステル化合物 (巳 1) The resin composition according to the present embodiment contains a thermosetting compound (Mitsumi). In the present specification, the thermosetting compound (Mitsumi) means a thermosetting compound other than the polyfunctional vinyl aromatic polymer (8). As the thermosetting compound (M), a cyana group, a vinyl group (however, a group that becomes a polyfunctional vinyl aromatic polymer, a maleimide group, and a nadiimide group are not included. A vinylphenyl group is preferable.), a maleimide group. Group, and a compound having at least one functional group selected from the group consisting of nadiimide groups are preferable, and a cyanate ester compound having a cyanato group (Min 1)
、 ビニル基 (好ましくはビニルフエニル基) を有する変性ポリフエニレンエ —テル化合物 (巳 2) 、 マレイミ ド基を有するマレイミ ド化合物 (巳3) 、 ナジイミ ド基を有するナジイミ ド化合物 (巳 4) がより好ましく、 シアナト 基を有するシアン酸エステル化合物 (巳 1) 、 ビニル基 (好ましくはビニル フエニル基) を有する変性ポリフエニレンエーテル化合物 (巳 2) 、 マレイ ミ ド基を有するマレイミ ド化合物 (巳 3) がさらに好ましい。 A modified polyphenylene ether compound having a vinyl group (preferably a vinylphenyl group) (Minami 2), a maleimide compound having a maleimide group (Minami 3), and a nadiimide compound having a nadiimide group (Minami 4) are more preferable, Further, cyanate ester compounds having a cyanato group (Minami 1), modified polyphenylene ether compounds having a vinyl group (preferably vinylphenyl group) (Minami 2), and maleimide compounds having a maleimide group (Minami 3) are further included. preferable.
[0034] «シアン酸エステル化合物 (巳 1) »
〇 2020/175537 13 卩(:171? 2020 /007686 [0034] «Cyanate ester compound (Mimi 1)» 〇 2020/175 537 13 卩 (:171? 2020 /007686
シアン酸エステル化合物はシアナト基を有する化合物の総称である。 本発 明で用いるシアン酸エステル化合物 (巳 1) は、 1分子中にシアナト基を 1 以上有することが好ましく、 2以上有することがより好ましい。 また、 シア ン酸エステル化合物 (巳 1) 1分子中のシアナト基の数の上限は、 1 2以下 であることが好ましく、 1 0以下であることがより好ましい。 また、 上述し たシアン酸エステル化合物 (巳 1) のシアナト基は、 芳香環に直接結合した シアナト基であることが好ましい。 The cyanate ester compound is a general term for compounds having a cyanato group. The cyanate ester compound (Mizu 1) used in the present invention preferably has one or more cyanato groups in one molecule, and more preferably has two or more cyanato groups. Further, the upper limit of the number of cyanato groups in one molecule of the cyanate ester compound (N 1) is preferably 12 or less, and more preferably 10 or less. Further, the cyanato group of the above-mentioned cyanate ester compound (Minami 1) is preferably a cyanato group directly bonded to the aromatic ring.
シアン酸エステル化合物 (巳 1) としては、 例えば、 ナフトールアラルキ ル型シアン酸エステル化合物 (ナフトールアラルキル型シアネート) 、 ナフ チレンエーテル型シアン酸エステル化合物、 フエノールノボラック型シアン 酸エステル化合物、 ビフエニルアラルキル型シアン酸エステル化合物、 ビス フエノール八型シアン酸エステル化合物、 ジアリルビスフエノール八型シア ン酸エステル化合物、 ビスフエノール IV!型シアン酸エステル化合物、 キシレ ン樹脂型シアン酸エステル化合物、 トリスフエノールメタン型シアン酸エス テル化合物、 およびアダマンタン骨格型シアン酸エステル化合物からなる群 より選択される少なくとも 1種が挙げられる。 これらの中でも、 ナフトール アラルキル型シアン酸エステル化合物、 ナフチレンエーテル型シアン酸エス テル化合物、 およびキシレン樹脂型シアン酸エステル化合物からなる群より 選択される少なくとも 1種であることが好ましく、 ナフトールアラルキル型 シアン酸エステル化合物であることがより好ましい。 これらのシアン酸エス テル化合物は、 公知の方法により調製してもよく、 市販品を用いてもよい。 Examples of the cyanate ester compound (Mitsumi 1) include naphthol aralkyl type cyanate ester compound (naphthol aralkyl cyanate), naphthylene ether type cyanate ester compound, phenol novolac type cyanate ester compound, and biphenyl aralkyl type. Cyanate ester compound, bisphenol octane cyanate ester compound, diallyl bisphenol octane cyanate ester compound, bisphenol IV! type cyanate ester compound, xylene resin cyanate ester compound, trisphenol methane cyanate At least one selected from the group consisting of an ester compound and an adamantane skeleton type cyanate compound is included. Among these, at least one selected from the group consisting of naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, and xylene resin type cyanate ester compounds is preferable, and naphthol aralkyl type cyanate compounds are preferable. More preferably, it is an acid ester compound. These cyanate ester compounds may be prepared by known methods, or commercially available products may be used.
[0035] シアン酸エステル化合物 (巳 1) としては、 下記式 (3 1) で示されるナ フトールアラルキル型シアン酸エステル化合物が挙げられる。 式 (3 1) で 示されるナフトールアラルキル型シアン酸エステル化合物は、
ナフトール あるいは /3 -ナフトール等のナフトール類と -キシリレングリコール、
« , -ジメ トキシ- -キシレン、 1 , 4—ジ(2 -ヒドロキシ _ 2—プロピル)ベ ンゼン等との反応により得られるナフトールアラルキル樹脂とハロゲン化シ アンとを縮合させて得られるものである。 その製法は特に限定されず、 シア
〇 2020/175537 14 卩(:171? 2020 /007686 [0035] Examples of the cyanate ester compound (N 1) include a naphthol aralkyl type cyanate ester compound represented by the following formula (3 1). The naphthol aralkyl-type cyanate compound represented by the formula (31) is Naphthol or naphthols such as /3-naphthol and -xylylene glycol, It is obtained by condensing a naphthol aralkyl resin obtained by the reaction with «, -dimethoxy- -xylene, 1, 4-di(2-hydroxy _ 2-propyl) benzene, etc. and a halogenated cyanide. .. The manufacturing method is not particularly limited. 〇 2020/175 537 14 卩 (:171? 2020 /007686
ン酸エステル合成として現存するいかなる方法で製造してもよい。 It may be produced by any existing method for acid ester synthesis.
[化 6] [Chemical 6]
式 (3 1) 中、 [¾ 〜[¾〇4はそれぞれ独立に水素原子またはメチル基を表 す。 门〇は 1から 1 0の数である。 n cが異なる化合物が 2種以上含まれてい てもよい。 In the formula (3 1), to display the [¾ ~ [¾_〇 4 each independently represent a hydrogen atom or a methyl group.门○ is a number from 1 to 10. Two or more compounds having different nc may be contained.
シアン酸エステル化合物 (巳 1) については、 特開 2 0 1 0 - 1 3 8 3 6 4号公報の段落 0 0 2 4および 0 0 2 5を参照することができ、 その内容は 本明細書に組み込まれる。 Regarding the cyanate ester compound (Mitsumi 1), it is possible to refer to paragraphs 0 0 2 4 and 0 0 2 5 of JP-A No. 2 0 1 0 1 3 8 3 6 4 and the contents thereof are described in this specification. Incorporated into.
[0036] «変性ポリフエニレンエーテル化合物 (巳 2) » [0036] «Modified polyphenylene ether compound (Mimi 2)»
熱硬化性化合物 (巳) は、 ビニル基 (好ましくはビニルフエニル基) を含 有する置換基により末端変性された変性ポリフエニレンエーテル化合物 (巳 2) であることが好ましい。 本発明で用いる変性ポリフエニレンエーテル化 合物 (巳 2) は、 1分子中にビニル基を 1以上有することが好ましく、 2以 上有することがより好ましい。 また、 変性ポリフエニレンエーテル化合物 ( 巳 2) 1分子中のビニル基の数の上限は、 5以下であることが好ましく、 3 以下であることがより好ましい。 The thermosetting compound (N) is preferably a modified polyphenylene ether compound (N 2) which is end-modified with a substituent having a vinyl group (preferably vinyl phenyl group). The modified polyphenylene ether compound (N2) used in the present invention preferably has one or more vinyl groups in one molecule, and more preferably has two or more vinyl groups. Further, the upper limit of the number of vinyl groups in one molecule of the modified polyphenylene ether compound (N 2) is preferably 5 or less, and more preferably 3 or less.
変性ポリフエニレンエーテル化合物 (巳 2) は、 例えば、 ポリフエニレン エーテルの末端の全部または一部が、 ビニル基ないしビニルフエニル基によ り末端変性された変性物である。 本明細書に言う 「ポリフエニレンエーテル 」 とは、 下記式 (X I) で表されるポリフエニレンエーテル骨格を有する化 合物をいう。 The modified polyphenylene ether compound (Mimi 2) is, for example, a modified product in which all or part of the terminals of polyphenylene ether is terminally modified with a vinyl group or a vinylphenyl group. The “polyphenylene ether” referred to in the present specification refers to a compound having a polyphenylene ether skeleton represented by the following formula (X I).
[0037]
〇 2020/175537 15 卩(:171? 2020 /007686 [0037] 〇 2020/175 537 15 卩 (:171? 2020 /007686
式 (X I) 中、 [¾24、 [¾25、 [¾26、 および[¾27は、 同一または異なっても よく、 炭素数 6以下のアルキル基、 アリール基、 ハロゲン原子、 または水素 原子を表す。 氺は結合位置を表す。 In formula (XI), [¾ 24 , [¾ 25 , [¾ 26 , and [¾ 27, which may be the same or different, represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom. .. The symbol represents the bonding position.
[0038] 変性ポリフエニレンェーテルは、 式 (乂 2) または式 (乂3) で表される 繰返し単位をさらに含んでもよい。 [0038] The modified polyphenylene ether may further include a repeating unit represented by the formula (2) or the formula (3).
[化 8] [Chemical 8]
同一または異なっても よく、 炭素数 6以下のアルキル基またはフエニル基である。 [¾31、 [¾32、
They may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. [¾ 31 , ¾ 32 ,
3は、 同一または異なってもよく、 水素原子、 炭素数 6以下のアルキル基また はフエニル基である。 氺は結合位置を表す。 3 may be the same or different and is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. The symbol represents the bonding position.
[化 9] [Chemical 9]
式 (乂3) 中、 [¾36、 [¾37、 [¾38、 [¾39、 [¾40、 [¾41、 [¾42、 [¾43は、 同一または異なってもよく、 水素原子、 炭素数 6以下のアルキル基またはフ エニル基である。 は、 炭素数 1以上 20以下の直鎖状、 分岐状または環状 の 2価の炭化水素である。 *は結合位置を表す。 In the formula (3), [¾ 36 , [¾ 37 , [¾ 38 , [¾ 39 , [¾ 40 , [¾ 41 , [¾ 42 , [¾ 43, may be the same or different, a hydrogen atom, An alkyl group or phenyl group having 6 or less carbon atoms. Is a linear, branched or cyclic divalent hydrocarbon having 1 to 20 carbon atoms. * Represents a bonding position.
[0039] 変性ポリフエニレンェーテル化合物 (巳 2) は、 一部または全部を、 ビニ
〇 2020/175537 16 卩(:171? 2020 /007686 [0039] The modified polyphenylene ether compound (Mitsumi 2) is partially or entirely 〇 2020/175 537 16 卩 (: 171-1? 2020/007686
ルベンジル基等のエチレン性不飽和基、 エポキシ基、 アミノ基、 ヒドロキシ 基、 メルカプト基、 カルボキシ基、 およびシリル基等で官能基化された変性 ポリフエニレンエーテルを用いることもできる。 これらは 1種または 2種以 上を組み合わせて用いてもよい。 末端がヒドロキシ基であるポリフエニレン エーテルとしては例えば、 3八巳 丨 〇イノべーティブプラスチックス社製 3 八 9 0等が挙げられる。 A modified polyphenylene ether functionalized with an ethylenically unsaturated group such as a rubenzyl group, an epoxy group, an amino group, a hydroxy group, a mercapto group, a carboxy group, and a silyl group can also be used. These may be used alone or in combination of two or more. Examples of the polyphenylene ether having a hydroxy group at its end include 389,900 manufactured by Innovative Plastics Co., Ltd.
[0040] 変性ポリフエニレンエーテル化合物 (巳 2) の製造方法は、 本発明の効果 が得られるものであれば特に限定されない。 例えば、 ビニルベンジル基で官 能基化されたものは、 2官能フエニレンエーテルオリゴマーとビニルベンジ ルクロライ ドを溶剤に溶解させ、 加熱撹拌下で塩基を添加して反応させた後 、 樹脂を固形化することで製造できる。 カルボキシ基で官能基化されたもの は、 例えばラジカル開始剤の存在下または非存在下において、 ポリフエニレ ンエーテルに不飽和カルボン酸やその官能基化された誘導体を溶融混練し、 反応させることによって製造される。 あるいは、 ポリフエニレンエーテルと 不飽和カルボン酸やその官能的誘導体とをラジカル開始剤存在下または非存 在下で有機溶剤に溶かし、 溶液下で反応させることによって製造される。 [0040] The method for producing the modified polyphenylene ether compound (Mitsumi 2) is not particularly limited as long as the effects of the present invention can be obtained. For example, for those functionalized with a vinylbenzyl group, the bifunctional phenylene ether oligomer and vinylbenzyl chloride are dissolved in a solvent, and a base is added under heating and stirring to react them, and then the resin is solidified. It can be manufactured. Those functionalized with a carboxy group are produced, for example, by melt-kneading an unsaturated carboxylic acid or a functionalized derivative thereof with polyphenylene ether in the presence or absence of a radical initiator and reacting them. It Alternatively, it is produced by dissolving a polyphenylene ether and an unsaturated carboxylic acid or a functional derivative thereof in an organic solvent in the presence or absence of a radical initiator, and reacting in a solution.
[0041 ] 変性ポリフエニレンエーテル化合物 (巳 2) は、 少なくとも一方の末端 ( 好ましくは両末端) にエチレン性不飽和基を有する変性ポリフエニレンエー テル (以下、 「変性ポリフエニレンエーテル (9) 」 ということがある) を 含むものであることが好ましい。 エチレン性不飽和基としては、 エテニル基 、 アリル基、 アクリロイル基、 メタクリロイル基、 プロべニル基、 ブテニル 基、 ヘキセニル基およびオクテニル基等のアルケニル基、 シクロペンテニル 基およびシクロヘキセニル基等のシクロアルケニル基、 ビニルフエニル基、 ビニルベンジル基およびビニルナフチル基等のアルケニルアリール基が挙げ られる。 両末端の 2つのエチレン性不飽和基は、 同一の官能基であってもよ いし、 異なる官能基であってもよい。 [0041] The modified polyphenylene ether compound (M2) is a modified polyphenylene ether having at least one terminal (preferably both terminals) having an ethylenically unsaturated group (hereinafter, referred to as "modified polyphenylene ether (9 )” may be included). Examples of the ethylenic unsaturated group include ethenyl group, allyl group, acryloyl group, methacryloyl group, probenyl group, butenyl group, alkenyl group such as hexenyl group and octenyl group, cycloalkenyl group such as cyclopentenyl group and cyclohexenyl group. And alkenylaryl groups such as vinylphenyl group, vinylbenzyl group and vinylnaphthyl group. The two ethylenically unsaturated groups at both ends may have the same functional group or different functional groups.
[0042] 変性ポリフエニレンエーテル (9) として式 (1) で表される構造が挙げ られる。
\¥0 2020/175537 17 卩(:17 2020 /007686 [0042] The modified polyphenylene ether (9) includes a structure represented by the formula (1). \\0 2020/175 537 17 (: 17 2020 /007686
[化 10] [Chemical 10]
式 ( 1) 中、 X 3は芳香族基を表し、 (丫3 -〇) 01はポリフエニレンエー テル部分を表し、
[¾ 2、 3はそれぞれ独立して水素原子、 アルキル基、 アルケニル基またはアルキニル基を表し、 01は 1〜 1 0 0の数を表し、 nは 1〜 6の数を表し、 は 1〜 4の数を表す。 好ましくは、
In the formula (1), X 3 represents an aromatic group, (丫3- 〇) 01 represents a polyphenylene ether moiety, [¾ 2 and 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, 01 represents a number of 1 to 100, n represents a number of 1 to 6, and 1 to 4 Represents the number of. Preferably,
素原子である。 好ましくは、 は 1以上 5 0以下の数であり、 より好ましく は、 1以上 3 0以下の数である。 好ましくは、 nは 1以上 4以下の数であり 、 さらに好ましくは、 门は 1 または 2であり、 一層好ましくは、 门は 1であ る。 また、 好ましくは、 は 1以上 3以下の数であり、 さらに好ましくは、 は 1 または 2であり、 一層好ましくは、 は 2である。 It is an elementary atom. It is preferably a number of 1 or more and 50 or less, and more preferably a number of 1 or more and 30 or less. Preferably, n is a number of 1 or more and 4 or less, more preferably 1 or 2, and more preferably 1 or 2. In addition, is preferably a number of 1 or more and 3 or less, more preferably 1 or 2, and even more preferably 2.
、 n、 9がそれぞれ異なる化合物が 2種以上含まれていてもよい。 , N and 9 may be different from each other.
[0043] 変性ポリフエニレンェーテル (9) は、 式 (2) で表されることが好まし い。 [0043] The modified polyphenylene ether (9) is preferably represented by the formula (2).
[化 1 1]
式 (2) における 8、
少なくともいずれか一方が 0でない、 〇〜 1 0 0の数を表す。 3および匕は、 好ましくは 1以上 5 0以下の数であり、 よ り好ましくは、 1以上 3 0以下の数である。 [Chemical 1 1] 8, in equation (2), Represents a number from 0 to 100, at least one of which is not 0. 3 and the swallow are preferably 1 or more and 50 or less, and more preferably 1 or more and 30 or less.
ここで、 一 (〇一X—〇) 一は、 式 (3) または式 (4) で表されること が好ましい。 3、 13が異なる化合物が 2種以上含まれていてもよい。
〇 2020/175537 18 卩(:171? 2020 /007686 Here, it is preferable that one (X1X-X)1 is represented by the formula (3) or the formula (4). Two or more kinds of compounds different in 3 and 13 may be contained. 〇 2020/175 537 18 卩 (:171? 2020 /007686
[化 12] [Chemical 12]
11は、 同一または異なってもよく 、 炭素数 6以下のアルキル基またはフエニル基である。 [¾7、
同 —または異なってもよく、 水素原子、 炭素数 6以下のアルキル基またはフエ ニル基である。 氺は結合位置を表す。 11 may be the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. [¾ 7 , They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. The symbol represents the bonding position.
[化 13] [Chemical 13]
式 (4) 中、 [¾12、 [¾13、 [¾14、 [¾15、 [¾16、 [¾17、 [¾18、 [¾19は、 同 —または異なってもよく、 水素原子、 炭素数 6以下のアルキル基またはフエ ニル基である。
は、 炭素数 20以下の直鎖状、 分岐状または環状の 2価の 炭化水素基である。 *は結合位置を表す。 In the formula (4), [¾ 12 , [¾ 13 , [¾ 14 , ][ ¾ 15 , [¾ 16 , [¾ 17 , [¾ 18 , and ¾ 19 may be the same or different, a hydrogen atom, An alkyl group or a phenyl group having 6 or less carbon atoms. Is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. * Represents a bonding position.
[0044] また、 式 (2) における一 (丫一〇) 一は、 式 (5) で表されることが好 ましい。 [0044] Further, it is preferable that the (1)-(1) in the formula (2) is represented by the formula (5).
[化 14] [Chemical 14]
式 (5) 中、 [¾22、 [¾23は、 同一または異なってもよく、 水素原子、 炭素 数 6以下のアルキル基またはフエニル基である。
[¾21は、 同一または 異なってもよく、 炭素数 6以下のアルキル基またはフエニル基である。
\¥02020/175537 19 卩(:17 2020 /007686 In formula (5), [¾ 22 and [¾ 23, which may be the same or different, are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. [ 21 may be the same or different and each represents an alkyl group having 6 or less carbon atoms or a phenyl group. \¥02020/175537 19 卩(: 17 2020 /007686
[0045] 式 (4) における八1としては、 例えば、 メチレン、 エチリデン、 1 -メチ ルエチリデン、 1 , 1 —プロピリデン、 2, 2—プロピリデン、 1 , 4—フ エニレンビス ( 1 -メチルエチリデン) 、 1 , 3 -フエニレンビス ( 1 -メ チルエチリデン) 、 シクロヘキシリデン、 フエニルメチレン、 ナフチルメチ レン、 1 -フエニルエチリデン等の 2価の有機基が挙げられるが、 これらに 限定されるものではない。 The eight 1 in [0045] Equation (4), for example, methylene, ethylidene, 1 - methylcarbamoyl Ruechiriden, 1, 1 - propylidene, 2, 2-propylidene, 1, 4-off Enirenbisu (1 - methylethylidene) 1 Examples thereof include, but are not limited to, divalent organic groups such as 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene.
[0046] 上記変性ポリフエニレンエーテルのなかでは、 [¾4、 [¾5、 [¾6、 [¾10、
[0046] Among the modified polyphenylene ethers described above, [¾ 4 , [¾ 5 , [¾ 6 , [¾ 10 ,
1、
が炭素数 3以下のアルキル基であり、
2、 [¾13、 [¾14、 [¾15、 [¾16、 [¾17、 [¾18、 [¾19、 [¾22、 23が水素原子また は炭素数 3以下のアルキル基であるポリフエニレンエーテルが好ましく、 特 に式 (3) または式 (4) で表される一 (〇一 X—〇) 一が、 式 (9) 、 式 (1 0) 、 および/または式 (1 1) であり、 式 ( 5) で表される一 (丫一 〇) 一が、 式 (1 2) または式 (1 3) であるか、 あるいは式 (1 2) と式 (1 3) がランダムに配列した構造であることがより好ましい。 1 , Is an alkyl group having 3 or less carbon atoms, 2, [¾ 13, [¾ 14, a [¾ 15, [¾ 16, [¾ 17, [¾ 18, [¾ 19, [¾ 22, 23 is a hydrogen atom or an alkyl group having 3 or less carbon atoms poly Phenylene ether is preferable, and in particular, one represented by formula (3) or formula (4) (○ 1 X — 〇) is represented by formula (9), formula (1 0), and/or formula (1 1 ), and one (丫110) one represented by the formula (5) is the formula (1 2) or the formula (1 3), or the formula (1 2) and the formula (1 3) are random. It is more preferable that the structure has a structure in which
[0047] [化 15] [0047] [Chemical 15]
式 (1 0) 中、
[¾45、 [^46、 [¾47は、 同一でも異なってもよく、 水 素原子またはメチル基である。 八2は、 炭素数 20以下の直鎖状、 分岐状また は環状の 2価の炭化水素基である。 *は結合位置である。 式 (1 0) 、 式 ( 1 1) 中の八2は、 式 (4) における八 1の具体例と同じものが具体例として 挙げられる。
〇 2020/175537 20 卩(:171? 2020 /007686 In formula (10), [¾45, [^46, [¾, which may be the same or different, are a hydrogen atom or a methyl group. Eighty- two is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. * Is the binding position. Specific examples of eighty- two in the formulas (10) and (11) are the same as the eighteenth one in the formula (4). 〇 2020/175 537 20 (:171? 2020/007686
[0048] 変性ポリフェニレンエーテル化合物 (巳 2) の◦ 〇法によるポリスチレ ン換算の数平均分子量は、 5 0 0以上 3 0 0 0以下であることが好ましい。 数平均分子量が上記下限値以上であることにより、 本実施形態の樹脂組成物 を塗膜状にする際にべたつきがより一層抑制される傾向にある。 数平均分子 量が上記上限値以下であることにより、 溶剤への溶解性がより一層向上する 傾向にある。 [0048] It is preferable that the modified polyphenylene ether compound (Mitsumi 2) has a polystyrene-reduced number average molecular weight of 5,000 or more and 3,000 or less according to the method. When the number average molecular weight is at least the above lower limit, the stickiness tends to be further suppressed when the resin composition of the present embodiment is formed into a coating film. When the number average molecular weight is not more than the above upper limit, the solubility in a solvent tends to be further improved.
また、 変性ポリフェニレンエーテル化合物 (巳 2) の〇 〇によるポリス チレン換算の重量平均分子量は、 8 0 0以上 1 0 0 0 0以下であることが好 ましく、 8 0 0以上 5 0 0 0以下であることがより好ましい。 前記下限値以 上とすることにより、 樹脂組成物の誘電率および誘電正接がより低くなる傾 向にあり、 上記上限値以下とすることにより、 溶剤への溶解性、 低粘度およ び成形性がより向上する傾向にある。 The modified polyphenylene ether compound (Mimi 2) preferably has a polystyrene-equivalent weight average molecular weight of 800 or more and 100 or less, and 800 or more and 500 or less. Is more preferable. When the content is less than the above lower limit, the dielectric constant and dielectric loss tangent of the resin composition tend to be lower, and when the content is less than the above upper limit, solubility in a solvent, low viscosity and moldability Tend to improve.
さらに、 変性ポリフェニレンエーテル化合物 (巳 2) の末端の炭素一炭素 不飽和二重結合当量は、 炭素一炭素不飽和二重結合 1つあたり 4 0 0〜 5 0 0 0 9であることが好ましく、 4 0 0 9 ~ 2 5 0 0 9であることがより好ま しい。 前記下限値以上とすることにより、 誘電率および誘電正接がより低く なる傾向にある。 上記上限値以下とすることにより、 溶剤への溶解性、 低粘 度および成形性がより向上する傾向にある。 Furthermore, the carbon-carbon unsaturated double bond equivalent at the terminal of the modified polyphenylene ether compound (Mitsumi 2) is preferably 400 to 500 0.99 per carbon-carbon unsaturated double bond, It is more preferable that it is 4 0 9 ~ 2 5 0 0 9. By setting the content to the above lower limit or more, the dielectric constant and the dielectric loss tangent tend to be lower. When the content is not more than the above upper limit, the solubility in solvent, the low viscosity and the moldability tend to be further improved.
[0049] 変性ポリフェニレンエーテル化合物 (巳 2) の製造方法は、 特に限定され ず、 例えば、 2官能性フェノール化合物と 1官能性フェノール化合物とを酸 化カップリングして 2官能性フェニレンエーテルオリゴマーを得る工程 (酸 化カップリングエ程) と、 得られる 2官能性フェニレンエーテルオリゴマー の末端フェノール性水酸基をビニルベンジルエーテル化する工程 (ビニルべ ンジルエーテル化工程) とにより製造できる。 また、 このような変性ポリフ ェニレンエーテル化合物 (巳 2) としては、 例えば、 三菱ガス化学 (株) 製 (〇 巳一 2 3 1: 1 2 0 0など) を用いることができる。 [0049] The method for producing the modified polyphenylene ether compound (Mitsumi 2) is not particularly limited, and for example, a bifunctional phenol compound and a monofunctional phenol compound are subjected to acid coupling to obtain a bifunctional phenylene ether oligomer. It can be produced by a step (oxidation coupling step) and a step of vinylbenzyl etherifying the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer (vinyl benzyl etherification step). Further, as such a modified polyphenylene ether compound (Minami 2), for example, Mitsubishi Gas Chemical Co., Inc. (○Miichi 1 2 3 1:1 2 0 0 etc.) can be used.
[0050] «マレイミ ド化合物 (巳 3) » [0050] «Maleimide compound (Mimi 3)»
マレイミ ド化合物 (巳3) は分子中に 1個以上マレイミ ド基を有する化合
〇 2020/175537 21 卩(:171? 2020 /007686 A maleimide compound (Mimi 3) is a compound that has one or more maleimide groups in the molecule. 〇 2020/175 537 21 卩 (: 171-1? 2020 /007686
物を指す。 本発明で用いるマレイミ ド化合物 (巳3) は、 1分子中にマレイ ミ ド基を 1以上有することが好ましく、 2以上有することがより好ましい。 また、 マレイミ ド化合物 (巳3) 1分子中のマレイミ ド基の数の上限は、 1 5以下であることが好ましく、 1 3以下であることがより好ましい。 中でも 分子中に 2個以上のマレイミ ド基を有するビスマレイミ ド化合物、 ポリマレ イミ ド化合物が好ましく、 4 , 4’ ージフエニルメタンマレイミ ド、 4 , 4 ’ ージフエニルエーテルビスマレイミ ド、 01—フエニレンビスマレイミ ド、Refers to something. The maleimide compound (3) used in the present invention preferably has one or more maleimide groups in one molecule, more preferably two or more. In addition, the upper limit of the number of maleimide groups in one molecule of the maleimide compound (Mitsumi 3) is preferably 15 or less, and more preferably 13 or less. Among them, bismaleimide compounds and polymaleimide compounds having two or more maleimide groups in the molecule are preferable, and 4,4'-diphenylmethane maleimide, 4,4'-diphenyl ether bismaleimide, 01— Phenylene bismaleimide,
1 , 6—ビスマレイミ ドー (2 , 2 , 4—トリメチル) ヘキサン、 下記式 ( 3 1) 〜 (3 4) のいずれかで表される構成単位を含む化合物であることが 一層好ましい。 It is more preferable that the compound is a compound containing a structural unit represented by any one of the following formulas (31) to (34): 1,6-bismaleimidane (2,2,4-trimethyl)hexane.
[化 16] [Chemical 16]
式 (3 1) 中、
および
はそれぞれ独立に、 水素原子 、 炭素数 1〜 8のアルキル基またはフエニル基を表す。 In formula (3 1), and Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group.
式 (3 1) 中、 [¾ 5 1、 [¾ 5 2、
および
それぞれ独立に、 メチル 基、 エチル基、 フエニル基または水素原子であることが好ましく、 水素原子 であることがより好ましい。 In the formula (3 1), [¾ 5 1 , [¾ 5 2 , and Each independently, preferably a methyl group, an ethyl group, a phenyl group or a hydrogen atom, and more preferably a hydrogen atom.
n 1は、 1〜 1 0の数であり、 1〜 4の数がより好ましい。 n 1が異なる 化合物が 2種以上含まれていてもよい。 n 1 is a number of 1 to 10, and a number of 1 to 4 is more preferable. Two or more compounds having different n 1 may be contained.
[0051 ]
\¥0 2020/175537 22 卩(:17 2020 /007686 [0051] \¥0 2020/175 537 22 (: 17 2020 /007686
[化 17] [Chemical 17]
7はそれぞれ独立に水素原子またはメチル基を表す。 Each 7 independently represents a hydrogen atom or a methyl group.
のうち、 1〜 3つがメチル基であり、 残りの 3〜 1つがエチル 基であることが好ましく、 4
のうち、 2つがメチル基であり、 残り の 2つがエチル基であることがより好ましい。 さらに、 2つの芳香族環につ いて、 それぞれ、 置換している
Of these, it is preferable that 1 to 3 are methyl groups and the remaining 3 to 1 are ethyl groups. Of these, two are more preferably methyl groups, and the remaining two are more preferably ethyl groups. In addition, each of the two aromatic rings is substituted.
がより好ましい。 Is more preferable.
[0052] [化 18] [0052] [Chemical 18]
基を表す。 Represents a group.
[0053] [化 19] [0053] [Chemical 19]
〇 2020/175537 23 卩(:171? 2020 /007686 式 (3 4) 中、
水素原子、 メチル基またはェチル 基を表す。 〇 2020/175537 23 ((171?2020/007686) formula (34), Represents a hydrogen atom, a methyl group or an ethyl group.
[0054] マレイミ ド化合物 (巳 3) の不飽和イミ ド基の当量は、 2 0 0 9 / 6 9以 上であることが好ましく、 また、 4 0 0
9以下であることが好ましい[0054] equivalents of unsaturated imide groups maleimide de Compound (Snake 3) is preferably from 2 0 0 9/6 9 than on, also 4 0 0 Preferably 9 or less
。 なおここでの当量は、 2種以上のマレイミ ド化合物を含む場合、 樹脂組成 物に含まれる各マレイミ ド化合物の質量を考慮した加重平均の不飽和イミ ド 基の当量とする。 .. In addition, when two or more maleimide compounds are contained, the equivalent here is the weighted average equivalent of unsaturated imide groups in consideration of the mass of each maleimide compound contained in the resin composition.
[0055] «ナジイミ ド化合物 (巳 4) » [0055] «Naziimide compound (Mimi 4)»
ナジイミ ド化合物 (巳 4) は、 分子内にナジイミ ド基を有する化合物であ る。 本発明で用いるナジイミ ド化合物 (巳4) は、 1分子中にナジイミ ド基 を 1以上有することが好ましく、 2以上有することがより好ましい。 また、 ナジイミ ド化合物 (巳 4) 1分子中のナジイミ ド基の数の上限は、 5以下で あることが好ましく、 3以下であることがより好ましい。 ナジイミ ド化合物 (巳 4) は、 より具体的には、 下記式 (N 1 ) または (N 2) で表される基 を有することが好ましい。 氺は結合位置を表す。 The nadiide compound (Mimi 4) is a compound having a nadiide group in its molecule. It is preferable that the nadiimide compound (Minami 4) used in the present invention has one or more nadiimide groups in one molecule, and more preferably two or more. Further, the upper limit of the number of nadiimide groups in one molecule of the nadiide compound (N 4) is preferably 5 or less, and more preferably 3 or less. More specifically, it is preferable that the namidide compound (Minami 4) has a group represented by the following formula (N 1) or (N 2 ). The symbol represents the bonding position.
[化 20] [Chemical 20]
、 はそれぞれ独立に、 水素原子ま たは炭素数 1 〜 6のアルキル基を表す。 And each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
[0056] ナジイミ ド化合物としては、 下記式 (N 3) で表される化合物がさらに好 ましい。
\¥0 2020/175537 24 ?01/1?2020/007686 As the nadiimide compound, a compound represented by the following formula (N 3) is more preferable. \\0 2020/175537 24 ?01/1?2020/007686
[化 21 ] [Chemical 21]
、 原子または炭素数 1〜 6のアルキ ル基を表し、
は、 炭素数 1〜 6のアルキレン基または芳香環を含む 2価の 連結基を示す。 芳香環を含む 2価の連結基としては、 フヱニレン基、 ビフエ ニレン基およびナフチレン基が例示される。 Represents an atom or an alkyl group having 1 to 6 carbon atoms, Represents a divalent linking group containing an alkylene group having 1 to 6 carbon atoms or an aromatic ring. Examples of the divalent linking group containing an aromatic ring include a phenylene group, a biphenylene group and a naphthylene group.
その他、 ナジイミ ド化合物 (巳 4) としては、 国際公開第 2 0 1 5 / 1 0 5 1 0 9号の段落 0 0 2 6〜 0 0 3 5の記載を参酌でき、 これらの内容は本 明細書に組み込まれる。 In addition, as the nazide compound (Mimi 4), the description in paragraphs 0 0 2 6 to 0 0 35 of International Publication No. 20 15/10 5 10 9 can be referred to, and the contents thereof are described in this specification. Incorporated into the book.
[0057] 本実施形態に係る樹脂組成物における樹脂成分の総量 1 0 0質量部に対す る、 熱硬化性化合物 (巳) の含有量は、 5質量部以上であることが好ましく 、 1 〇質量部以上であることがより好ましく、 1 5質量部以上であることが さらに好ましく、 2 0質量部以上であることが一層好ましい。 上限値として は、 9 5質量部以下であることが好ましく、 8 0質量部以下であることがよ り好ましく、 7 0質量部以下であることがさらに好ましい。 [0057] The content of the thermosetting compound (M) is preferably 5 parts by mass or more based on 100 parts by mass of the resin component in the resin composition according to the present embodiment, and 10 parts by mass. It is more preferably at least 15 parts by mass, more preferably at least 15 parts by mass, still more preferably at least 20 parts by mass. The upper limit is preferably 95 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less.
また、 多官能ビニル芳香族重合体 (八) 1 0 0質量部に対し、 1質量部以 上であることが好ましく、 1 0質量部以上であることがより好ましく、 2 0 質量部以上であることがさらに好ましい。 上限値としては、 1 9 0 0質量部 以下であることが好ましく、 9 0 0質量部以下であることがより好ましく、 4 0 0質量部以下であることがさらに好ましく、 1 2 0質量部以下であって もよく、 8 0質量部以下であってもよく、 6 0質量部以下であってもよい。 樹脂組成物は、 熱硬化性化合物 (巳) を、 1種のみ含んでいてもよいし、 Further, with respect to 100 parts by mass of the polyfunctional vinyl aromatic polymer (8), 1 part by mass or more is preferable, 10 parts by mass or more is more preferable, and 20 parts by mass or more. Is more preferable. The upper limit value is preferably 1900 parts by mass or less, more preferably 900 parts by mass or less, further preferably 400 parts by mass or less, and 120 parts by mass or less. Or may be 80 parts by mass or less, or 60 parts by mass or less. The resin composition may contain only one thermosetting compound (Mitsumi),
2種以上含んでいてもよい。 2種以上含む場合、 合計量が上記範囲となるこ とが好ましい。
〇 2020/175537 25 卩(:171? 2020 /007686 You may include 2 or more types. When two or more kinds are included, the total amount is preferably within the above range. 〇 2020/175 537 25 (:171? 2020 /007686
[0058] 本実施形態に係る樹脂組成物は、 後述する充填材 (〇 を含まない場合、 樹脂成分が樹脂組成物の 9 0質量%以上を占めることが好ましく、 9 5質量 %以上を占めることがより好ましく、 9 8質量%以上を占めることがさらに 好ましい。 [0058] In the resin composition according to the present embodiment, it is preferable that the resin component occupy 90% by mass or more of the resin composition (when ◯ is not contained, the amount is 95% by mass or more). Is more preferable, and it is still more preferable that it accounts for 98% by mass or more.
本実施形態に係る樹脂組成物は、 充填材 (<3) を含む場合、 樹脂成分が樹 脂組成物の 1 5質量%以上を占めることが好ましく、 2 0質量%以上を占め ることがより好ましく、 3 0質量%以上を占めることがさらに好ましい。 ま た、 上限値としては、 樹脂成分が樹脂組成物の 9 0質量%以下を占めること が好ましく、 8 5質量%以下を占めることがより好ましく、 8 0質量%以下 を占めることがさらに好ましい。 When the resin composition according to the present embodiment includes a filler (<3), the resin component preferably accounts for 15% by mass or more of the resin composition, and more preferably 20% by mass or more. It is more preferable that the amount of this component be 30% by mass or more. Further, as the upper limit value, it is preferable that the resin component accounts for 90% by mass or less of the resin composition, more preferably 85% by mass or less, and further preferably 80% by mass or less.
[0059] <ラジカル重合開始剤> <Radical polymerization initiator>
本実施形態に係る樹脂組成物は、 ラジカル重合開始剤を含まない。 ここで 「含まない」 とは、 積極的に配合しないことを意味し、 不純物等が意図せず に配合される場合まで含む趣旨ではない。 不純物等意図せずに配合される場 合とは、 例えば、 質量基準で、 4 〇1以下であり、 さらには 1 以下 である。 本発明では、 0 であることが好ましい。 The resin composition according to this embodiment does not contain a radical polymerization initiator. Here, "does not contain" means not to be positively mixed, and does not mean that impurities and the like are mixed unintentionally. For example, when impurities are mixed unintentionally, it is, for example, not more than 401, and even less than 1 on a mass basis. In the present invention, it is preferably 0.
ラジカル重合開始剤の種類は特に限定されず、 熱ラジカル重合開始剤およ び光ラジカル重合開始剤が挙げられる。 The type of radical polymerization initiator is not particularly limited, and examples thereof include a thermal radical polymerization initiator and a photo radical polymerization initiator.
ラジカル重合開始剤として具体的には、 ペルオキシド (過酸化物) 、 アゾ 化合物、 ベンゾイン化合物、 アセトフエノン化合物、 アントラキノン化合物 、 チオキサントン化合物、 ケタール化合物、 ベンゾフエノン化合物、 ホスフ ィンォキサイ ド化合物が挙げられる。 Specific examples of the radical polymerization initiator include peroxides, azo compounds, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, and phosphinoxide compounds.
ペルオキシドは分子内にペルオキシ基 (一〇一〇一) を有する化合物が挙 げられ、 1—ブチルペルオキシ基を有する化合物やクミルペルオキシ基を有 する化合物、 ベンゾイルペルォキシ基を有する化合物が好ましい。 具体例と しては、 ベンゾイルペルオキシド (巳 〇) 、 _クロロべンゾイルぺルオ キシド、 ジクミルペルオキシド (¢1 丨 〇リ ) 、 ジ_ 1—ブチルペルオキシ ド、 ジイソプロピルペルオキシカーボネート、 2 , 5—ジメチルー 2 , 5 -
〇 2020/175537 26 卩(:171? 2020 /007686 Examples of peroxides include compounds having a peroxy group (10,101) in the molecule, and compounds having a 1-butylperoxy group, a compound having a cumylperoxy group, and a compound having a benzoylperoxy group are preferable. .. Specific examples include benzoyl peroxide (M), _ chlorobenzoyl peroxide, dicumyl peroxide (¢1), di_1-butylperoxide, diisopropylperoxycarbonate, 2,5-dimethyl- twenty five - 〇 2020/175 537 26 卩 (:171? 2020 /007686
ジー I _ブチルペルオキシヘキシン (0丫巳 ) 、 2 , 5—ジメチルー 2 ,Gee I _ Butylperoxyhexyne (0丫巳 ), 2, 5—Dimethyl-2,
5 -ジー I -ブチルペルオキシヘキサンが挙げられる。 市販品としては、 日 油社製の、 パーブチル!· I、 パーブチル 、 パーブチル 、 パークミル!· I、 パークミル 、 パークミルロ、 パーオクタ!· I、 パーへキサ 2 5巳、 などが挙 げられる。 5-D-I-butylperoxyhexane may be mentioned. Commercially available products include Perbutyl! I, Perbutyl, Perbutyl, Parkmill! I, Parkmill, Parkmillo, Perocta! I, Perhexa 25, manufactured by NOF CORPORATION.
アゾ化合物は分子内にアゾ基 (一 = 1\1 _) を有する化合物を指し、 具体 的には、 アゾビスイソプチロニトリル (八 丨 巳1\1) が挙げられる。 市販品と しては、 富士フイルム和光純薬製の八 丨 巳1\1、 V - 7 0 , ー6 5などが挙 げられる。 The azo compound refers to a compound having an azo group (1 = 1\1 _) in the molecule, and specific examples thereof include azobisisoptyronitrile (Hachiman 1\1). Examples of commercially available products include Fujifilm Wako Pure Chemical Industries' Yasumi 1\1, V-70, -65.
また、 過酸化物ではないが、 2 , 3 -ジメチルー 2 , 3 -ジフエニルブタ ンもラジカル重合開始剤として挙げられる。 市販品としてはノフマー巳〇一 9 0などが挙げられる。 Also, although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane is also mentioned as a radical polymerization initiator. Examples of commercially available products include Nofmer Mitsumi 910.
さらに、 国際公開第 2 0 1 3 / 0 4 7 3 0 5号の段落 0 0 4 2に記載のラ ジカル重合開始剤も例示され、 これらの内容は本明細書に組み込まれる。 一方、 本実施形態に係る樹脂組成物は、 カチオン重合開始剤を含まない構 成とすることもできる。 さらに、 本実施形態に係る樹脂組成物は、 光重合開 始剤を含まない構成とすることもできる。 Further, the radical polymerization initiator described in paragraph 0 042 of International Publication No. WO 201 3/0 4 7 3 05 is also exemplified, and the contents thereof are incorporated in the present specification. On the other hand, the resin composition according to this embodiment may be configured not to contain a cationic polymerization initiator. Furthermore, the resin composition according to the present embodiment may be configured to contain no photopolymerization initiator.
[0060] <充填材 (〇 > [0060] <Filler (〇)
本実施形態に係る樹脂組成物は、 低誘電率、 低誘電正接、 耐燃性および低 熱膨張性の向上のため、 充填材 (<3) を含むことが好ましく、 無機充填材が 好ましい。 使用される充填材 (<3) としては、 公知のものを適宜使用するこ とができ、 その種類は特に限定されず、 当業界において一般に使用されてい るものを好適に用いることができる。 具体的には、 天然シリカ、 溶融シリカ 、 合成シリカ、 アモルファスシリカ、 アエロジル、 中空シリカ等のシリカ類 、 ホワイ トカーボン、 チタンホワイ ト、 酸化亜鉛、 酸化マグネシウム、 酸化 ジルコニウム、 窒化ホウ素、 凝集窒化ホウ素、 窒化ケイ素、 窒化アルミニウ ム、 硫酸バリウム、 水酸化アルミニウム、 水酸化アルミニウム加熱処理品 ( 水酸化アルミニウムを加熱処理し、 結晶水の一部を減じたもの) 、 ベーマイ
〇 2020/175537 27 卩(:171? 2020 /007686 The resin composition according to the present embodiment preferably contains a filler (<3) in order to improve low dielectric constant, low dielectric loss tangent, flame resistance and low thermal expansion, and an inorganic filler is preferable. As the filler (<3) used, a known filler can be appropriately used, and the type thereof is not particularly limited, and those generally used in the art can be preferably used. Specifically, natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica and other silicas, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, nitride. Silicon, Aluminum Nitride, Barium Sulfate, Aluminum Hydroxide, Aluminum Hydroxide Heat Treated Product (Aluminum Hydroxide Heat Treated to Reduce Part of Crystal Water), Boehmai 〇 2020/175 537 27 卩 (: 171? 2020 /007686
卜、 水酸化マグネシウム等の金属水和物、 酸化モリブデンやモリブデン酸亜 鉛等のモリブデン化合物、 ホウ酸亜鉛、 錫酸亜鉛、 アルミナ、 クレー、 カオ リン、 タルク、 焼成クレー、 焼成カオリン、 焼成タルク、 マイカ、 巳ーガラ ス、 八ーガラス、 巳ーガラス、 〇ーガラス、 !_—ガラス、
ガラス、 3 -ガラス、 IV! -ガラス 0 2 0、 ガラス短繊維 (巳ガラス、 丁ガラス、 〇ガラ ス、 3ガラス、 〇ガラス等のガラス微粉末類を含む。 ) 、 中空ガラス、 球状 ガラスなど無機系の充填材の他、 スチレン型、 ブタジエン型、 アクリル型な どのゴムパウダー、 コアシェル型のゴムパウダー、 シリコーンレジンパウダ —、 シリコーンゴムパウダー、 シリコーン複合パウダーなど有機系の充填材 などが挙げられる。 Toluene, metal hydrate such as magnesium hydroxide, molybdenum compound such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, Mica, Mina Glass, Eight Glass, Mitsu Glass, O Glass,! _—Glass, Glass, 3-Glass, IV!-Glass 0 200, short glass fibers (including fine glass powders such as Mitsu Glass, Cho Glass, 0 glass, 3 glass, 0 glass), hollow glass, spherical glass, etc. In addition to inorganic fillers, styrene-type, butadiene-type, acrylic-type rubber powders, core-shell type rubber powders, silicone resin powders, silicone rubber powders, organic fillers such as silicone composite powders, and the like can be mentioned.
これらの中でも、 シリカ、 水酸化アルミニウム、 ベーマイ ト、 酸化マグネ シウムおよび水酸化マグネシウムからなる群から選択される 1種または 2種 以上が好適であり、 シリカがより好ましい。 シリカは、 球状のシリカが好ま しい。 球状シリカは、 また、 中空シリカであってもよい。 Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are preferable, and silica is more preferable. The silica is preferably spherical silica. The spherical silica may also be hollow silica.
これらの充填材を使用することで、 樹脂組成物の熱膨張特性、 寸法安定性 、 難燃性などの特性が向上する。 The use of these fillers improves the properties of the resin composition such as thermal expansion properties, dimensional stability, and flame retardancy.
[0061 ] 本実施形態に係る樹脂組成物における充填材 (〇 の含有量は、 所望する 特性に応じて適宜設定することができ、 特に限定されないが、 樹脂組成物中 の樹脂成分の総量を 1 〇〇質量部とした場合、 1 〇質量部以上であることが 好ましく、 2 0質量部以上であることがより好ましく、 3 0質量部以上であ ることがさらに好ましく、 5 0質量部以上であってもよい。 上限値としては 、 5 0 0質量部以下であることが好ましく、 4 0 0質量部以下であることが より好ましく、 3 0 0質量部以下であることがさらに好ましく、 2 5 0質量 部以下であることが一層好ましく、 2 0 0質量部以下であってもよい。 充填材 (<3) は 1種を用いても 2種以上を用いてもよい。 2種以上を用い る場合はその合計量が上記の範囲となることが好ましい。 [0061] The content of the filler (○ in the resin composition according to the present embodiment can be appropriately set according to the desired characteristics, and is not particularly limited, but the total amount of the resin components in the resin composition is 1 In the case of XX parts by mass, it is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, and 50 parts by mass or more. The upper limit is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, further preferably 300 parts by mass or less, and 25 The content is more preferably 0 parts by mass or less, and may be 200 parts by mass or less.The filler (<3) may be used singly or in combination of two or more. In that case, the total amount is preferably within the above range.
[0062] <他の樹脂成分> [0062] <Other resin components>
本実施形態に係る樹脂組成物は、 上述した多官能ビニル芳香族重合体 (八
〇 2020/175537 28 卩(:171? 2020 /007686 The resin composition according to the present embodiment is a polyfunctional vinyl aromatic polymer (8 〇 2020/175 537 28 卩 (:171? 2020 /007686
) および熱硬化性化合物 (巳) 以外の他の樹脂成分を含んでいてもよい。 他 の樹脂成分としては、 エポキシ樹脂、 フヱノール樹脂、 オキセタン樹脂、 ベ ンゾオキサジン化合物、 重合可能な不飽和基を有する化合物、 エラストマー および活性エステル化合物よりなる群から選択される 1種以上が例示される 本実施形態に係る樹脂組成物においては、 樹脂成分中の多官能ビニル芳香 族重合体 ( ) および熱硬化性化合物 (巳) の合計含有量が、 5 0質量%以 上であることが好ましく、 7 0質量%以上であることが好ましく、 8 0質量 %以上であることがより好ましく、 9 0質量%以上であることがさらに好ま しく、 9 5質量%以上であってもよく、 9 7質量%以上であってもよく、 9 8質量%以上であってもよい。 ) And a thermosetting compound (Mitsumi), other resin components may be included. Examples of the other resin component include one or more selected from the group consisting of epoxy resin, phenol resin, oxetane resin, benzoxazine compound, compound having a polymerizable unsaturated group, elastomer and active ester compound. In the resin composition according to the embodiment, the total content of the polyfunctional vinyl aromatic polymer () and the thermosetting compound (M) in the resin component is preferably 50% by mass or more, It is preferably 0% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 95% by mass or more, 97% by mass. It may be more than 90% by mass.
[0063] <硬化促進剤 (触媒) > <Curing accelerator (catalyst)>
本実施形態に係る樹脂組成物は、 硬化促進剤をさらに含んでもよい。 硬化 促進剤としては、 特に限定されないが、 例えば、 有機金属塩類 (例えば、 才 クチル酸亜鉛、 ナフテン酸亜鉛、 ナフテン酸コバルト、 ナフテン酸銅、 アセ チルアセトン鉄、 オクチル酸ニッケル、 オクチル酸マンガン等) 、 フエノー ル化合物 (例えば、 フエノール、 キシレノール、 クレゾール、 レゾルシン、 カテコール、 オクチルフエノール、 ノニルフエノール等) 、 アルコール類 ( 例えば、 1 —ブタノール、 2—エチルへキサノール等) 、 イミダゾール類 ( 例えば、 2—メチルイミダゾール、 2—エチルー 4—メチルイミダゾール、 The resin composition according to this embodiment may further include a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include organic metal salts (for example, zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetoneacetone, nickel octylate, manganese octylate, etc.), Phenol compounds (eg phenol, xylenol, cresol, resorcin, catechol, octylphenol, nonylphenol etc.), alcohols (eg 1-butanol, 2-ethylhexanol etc.), imidazoles (eg 2-methylimidazole) , 2-ethyl-4-methylimidazole,
2—フエニルイミダゾール、 1 —シアノエチルー 2—フエニルイミダゾール 、 1 —シアノエチルー 2—エチルー 4—メチルイミダゾール、 2—フエニル - 4 , 5—ジヒドロキシメチルイミダゾール、 2—フエニルー 4—メチルー 5—ヒドロキシメチルイミダゾール等) 、 およびこれらのイミダゾール類の カルボン酸若しくはその酸無水類の付加体等の誘導体、 アミン類 (例えば、 ジシアンジアミ ド、 ベンジルジメチルアミン、 4—メチルー 1\1 , 1\1 _ジメチ ルベンジルアミン等) 、 リン化合物 (例えば、 ホスフィン系化合物、 ホスフ ィンオキシド系化合物、 ホスホニウム塩系化合物、 ダイホスフィン系化合物
〇 2020/175537 29 卩(:171? 2020 /007686 2-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1-cyanoethyl-2-ethyl-4-methyl imidazole, 2-phenyl-4,5-dihydroxymethyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, etc. ), and derivatives of these imidazoles such as carboxylic acids or adducts of their acid anhydrides, amines (eg, dicyandiamide, benzyldimethylamine, 4-methyl-1\1, 1\1 _dimethylbenzylamine, etc.) ), phosphorus compounds (eg, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine compounds 〇 2020/175 537 29 卩 (:171? 2020 /007686
等) 、 エポキシーイミダゾールアダクト系化合物が挙げられる。 Etc.), and epoxy-imidazole adduct compounds.
好ましい硬化促進剤は、 イミダゾール類および有機金属塩であり、 イミダ ゾール類がより好ましい。 Preferred curing accelerators are imidazoles and organic metal salts, with imidazoles being more preferred.
[0064] 硬化促進剤の含有量は、 含有する場合、 下限値は、 樹脂組成物中の樹脂成 分の総量 1 0 0質量部に対し、 〇. 0 0 5質量部以上であることが好ましく 、 〇. 0 1質量部以上であることがより好ましく、 〇. 1質量部以上である ことがさらに好ましい。 また、 前記硬化促進剤の含有量の上限は、 樹脂組成 物中の樹脂成分の総量 1 〇〇質量部に対し、 1 〇質量部以下であることが好 ましく、 5質量部以下であることがより好ましく、 2質量部以下であること がさらに好ましい。 When the content of the curing accelerator is contained, the lower limit is preferably 0.005 parts by mass or more based on 100 parts by mass of the total amount of the resin components in the resin composition. , 0.01 parts by mass or more is more preferable, and 0.1 parts by mass or more is further preferable. Further, the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, and 5 parts by mass or less based on 100 parts by mass of the total amount of the resin components in the resin composition. Is more preferable, and even more preferably 2 parts by mass or less.
硬化促進剤は、 1種を単独で、 または 2種以上を組み合わせて用いること ができる。 2種以上用いる場合は、 合計量が上記範囲となる。 The curing accelerators may be used alone or in combination of two or more. When using 2 or more types, the total amount is within the above range.
[0065] <溶剤> [0065] <Solvent>
本実施形態に係る樹脂組成物は、 溶剤を含有してもよく、 有機溶剤を含有 することが好ましい。 この場合、 本実施形態に係る樹脂組成物は、 上述した 各種樹脂成分の少なくとも一部、 好ましくは全部が溶剤に溶解または相溶し た形態 (溶液またはワニス) である。 溶剤としては、 上述した各種樹脂成分 の少なくとも一部、 好ましくは全部を溶解または相溶可能な極性有機溶剤ま たは無極性有機溶剤であれば特に限定されず、 極性有機溶剤としては、 例え ば、 ケトン類 (例えば、 アセトン、 メチルエチルケトン、 メチルイソプチル ケトン等) 、 セロソルブ類 (例えば、 プロピレングリコールモノメチルエー テル、 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) 、 エステル 類 (例えば、 乳酸エチル、 酢酸メチル、 酢酸エチル、 酢酸プチル、 酢酸イソ アミル、 乳酸エチル、 メ トキシプロピオン酸メチル、 ヒドロキシイソ酪酸メ チル等) アミ ド類 (例えば、 ジメ トキシアセトアミ ド、 ジメチルホルムアミ ド類等) が挙げられ、 無極性有機溶剤としては、 芳香族炭化水素 (例えば、 トルエン、 キシレン等) が挙げられる。 The resin composition according to this embodiment may contain a solvent, and preferably contains an organic solvent. In this case, the resin composition according to the present embodiment is in a form (solution or varnish) in which at least a part, preferably all of the various resin components described above are dissolved or compatible with a solvent. The solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent capable of dissolving or compatibilizing at least a part, preferably all, of the various resin components described above, and examples of the polar organic solvent include: , Ketones (eg, acetone, methyl ethyl ketone, methyl isoptyl ketone, etc.), cellosolves (eg, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (eg, ethyl lactate, methyl acetate, ethyl acetate, Butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.) Amides (for example, dimethoxyacetamide, dimethylformamides, etc.), and nonpolar organic solvents include And aromatic hydrocarbons (eg, toluene, xylene, etc.).
溶剤は、 1種を単独で、 または 2種以上を組み合わせて用いることができ
\¥02020/175537 30 卩(:17 2020 /007686 The solvents may be used alone or in combination of two or more. \¥02020/175537 30 卩 (: 17 2020 /007686
る。 It
[0066] <その他の成分> [0066] <Other ingredients>
本実施形態に係る樹脂組成物は、 本発明の効果を阻害しない範囲で、 上記 の成分の他、 難燃剤、 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、 流動調整剤、 滑剤、 消泡剤、 分散剤、 レべリング剤、 光沢剤、 重合禁止剤、 シランカップリング剤等を含んでもよい。 これらの添 加剤は、 1種を単独で、 または 2種以上を組み合わせて用いることができる The resin composition according to the present embodiment contains, in a range that does not impair the effects of the present invention, a flame retardant, an ultraviolet absorber, an antioxidant, a fluorescent whitening agent, a photosensitizer, a dye, a pigment, in addition to the above components. , A thickener, a flow control agent, a lubricant, an antifoaming agent, a dispersant, a leveling agent, a brightening agent, a polymerization inhibitor, a silane coupling agent, etc. These additives may be used alone or in combination of two or more.
[0067] <樹脂組成物の物性> <Physical properties of resin composition>
本実施形態に係る樹脂組成物は、 ·! . 6 〇!厚の板状の硬化物に成形した とき、 1 0◦ 1~12における誘電率 (01<) を 2. 6以下とすることができ、 2. 5以下とすることもできる。 前記誘電率の下限値は、 1. 0が理想であ るが、 2. 1以上が実際的である。 The resin composition according to the present embodiment is...! .6 〇! When molded into a plate-shaped cured product, the dielectric constant (01<) at 10°C 1 to 12 can be 2.6 or less, or 2.5 or less. The ideal lower limit of the dielectric constant is 1.0, but 2.1 or more is practical.
また、 本実施形態に係る樹脂組成物は、 ·! . 6 〇!厚の板状の硬化物に成 形したとき、 1 0◦ 1~12における誘電正接 (0干) を〇. 0030以下とす ることができ、 〇. 0025以下とすることもでき、 〇. 0020以下とす ることもでき、 0. 001 5以下とすることもできる。 前記誘電率の下限値 は、 0が理想であるが、 〇. 0001以上が実際的である。 In addition, the resin composition according to the present embodiment is...! .6 〇! When formed into a thick plate-like cured product, the dielectric loss tangent (0 degree) at 10 ◦ 1 to 12 can be 〇.0030 or less, and can also be 〇.0025 or less. Yes, it can be less than 0.0000, or less than 0.0015. The lower limit of the dielectric constant is ideally 0, but practically 0.0001 or more.
誘電率および誘電正接は、 後述する実施例に記載の方法で測定される。 The dielectric constant and the dielectric loss tangent are measured by the methods described in Examples below.
[0068] 本発明の好ましい実施形態に係る樹脂組成物においては、 低い熱膨張係数 (〇丁巳) を実現することができる。 例えば、 」 丨 3 0 6481 5. [0068] In the resin composition according to the preferred embodiment of the present invention, a low coefficient of thermal expansion (Octomi) can be realized. For example,''
1 9 に規定された〇丁巳 ( 〇!/。〇) でいうと、 75以下であることが 好ましく、 72以下であることがより好ましく、 70以下であることがさら に好ましい。 下限値は特に制限されないが、 50以上であることが実際的で ある。 In terms of 〇Cho (○!/. 〇) defined in 19 above, it is preferably 75 or less, more preferably 72 or less, and even more preferably 70 or less. The lower limit is not particularly limited, but it is practically 50 or more.
[0069] 本実施形態に係る樹脂組成物は、 ·! . 6 〇!厚の板状の硬化物に成形した とき、 ガラス転移温度を 230°〇以上とすることができ、 235°〇以上とす ることもでき、 240°〇以上とすることもできる。 前記ガラス転移温度の上
〇 2020/175537 31 卩(:171? 2020 /007686 [0069] The resin composition according to the present embodiment is...! .6 〇! When molded into a thick plate-like cured product, the glass transition temperature can be 230° 〇 or higher, 235° 〇 or higher, and 240 ° 〇 or higher. .. Above the glass transition temperature 〇 2020/175 537 31 卩 (:171? 2020 /007686
限値は、 特に定めるものではないが、 4 0 0 °〇以下、 さらには、 3 5 0 °〇以 下が実際的である。 Kirichi is not specifically limited, 4 0 0 ° 〇 less, further, 3 5 0 ° 〇 hereinafter is practical.
本実施形態に係る樹脂組成物は、 また、 1 . 6 〇!厚の板状の硬化物に成 形したとき、 ガラス転移温度が、 かかる樹脂組成物に含まれる樹脂成分の 1 質量%に相当する量の熱ラジカル重合開始剤 (例えば、 日油社製、 パープチ ル (商品名) ) を配合した樹脂組成物から形成される 1 .
板状の硬化物のガラス転移温度よりも、 8 °〇以上高いことが好ましく、 1 0 °〇以上高いことがより好ましい。 上限値としては、 例えば、 2 5 °〇以下であ る。 The resin composition according to this embodiment has a glass transition temperature of 1% by mass of the resin component contained in the resin composition when formed into a plate-like cured product having a thickness of 1.6! Formed from a resin composition containing an amount of a thermal radical polymerization initiator (for example, Papillyl (trade name) manufactured by NOF CORPORATION) 1. The glass transition temperature of the plate-shaped cured product is preferably 8 ° or higher, more preferably 10° or higher. The upper limit is, for example, 25° or less.
ガラス転移温度は、 後述する実施例に記載の方法で測定される。 The glass transition temperature is measured by the method described in Examples below.
[0070] <樹脂組成物の製造方法> <Method for producing resin composition>
本実施形態に係る樹脂組成物は、 常法によって製造することができる。 例 えば、 多官能ビニル芳香族重合体 (八) と熱硬化性化合物 (巳) とを混合す る態様が挙げられる。 このときの好ましい含有量は上記で述べたとおりであ る。 また、 本実施形態に係る樹脂組成物においては、 さらに、 充填材 (〇) や他の樹脂成分、 その他の添加剤を適宜共存させて混練等を行ってもよい。 他の樹脂成分を配合することにより、 外観を向上させたり、 その他の特性を 良化させたりしてもよい。 The resin composition according to this embodiment can be manufactured by a conventional method. For example, a mode in which the polyfunctional vinyl aromatic polymer (8) and the thermosetting compound (Mitsumi) are mixed can be mentioned. The preferable content at this time is as described above. In addition, in the resin composition according to the present embodiment, kneading and the like may be performed by appropriately coexisting the filler (◯), other resin components, and other additives. By adding other resin components, the appearance may be improved or other characteristics may be improved.
本実施形態に係る樹脂組成物の一例は、 溶剤を含むワニスである。 また、 本実施形態に係る樹脂組成物の他の一例は、 板状の硬化物やフィルムである 。 さらに、 本実施形態に係る樹脂組成物は、 後述する用途に好ましく用いら れる。 An example of the resin composition according to this embodiment is a varnish containing a solvent. Another example of the resin composition according to the present embodiment is a plate-shaped cured product or film. Furthermore, the resin composition according to this embodiment is preferably used for the applications described below.
[0071 ] <用途> [0071] <Use>
本実施形態に係る樹脂組成物は、 硬化物として用いることができる。 具体 的には、 本実施形態の樹脂組成物は、 低誘電率材料および/または低誘電正 接材料として、 プリント配線板の絶縁層、 半導体パッケージ用材料として好 適に用いることができる。 本実施形態の樹脂組成物は、 プリプレグ、 プリプ レグから形成された金属箔張積層板、 樹脂複合シート、 およびプリント配線
〇 2020/175537 32 卩(:171? 2020 /007686 The resin composition according to this embodiment can be used as a cured product. Specifically, the resin composition of the present embodiment can be preferably used as a low dielectric constant material and/or a low dielectric loss tangent material, as an insulating layer of a printed wiring board, or as a semiconductor package material. The resin composition of the present embodiment includes a prepreg, a metal foil-clad laminate formed from the prepreg, a resin composite sheet, and a printed wiring. 〇 2020/175 537 32 卩 (:171? 2020 /007686
板を構成する材料として好適に用いることができる。 It can be suitably used as a material forming the plate.
本実施形態に係る樹脂組成物は、 これを用いて層状の成形品としたとき、 その厚さは、 5 01以上であることが好ましく、 1 〇 以上であることが より好ましい。 上限値としては、 2 01 01以下であることが好ましく、 1 01 111 以下であることがより好ましい。 なお、 上記層状の成形品の厚さは、 例えば 、 本実施形態の樹脂組成物をガラスクロス等に含浸させたものである場合、 ガラスクロスを含む厚さを意味する。 When the resin composition according to the present embodiment is formed into a layered molded product using the resin composition, the thickness thereof is preferably 501 or more, more preferably 10 or more. The upper limit is preferably 201 01 or less, more preferably 110 11 111 or less. The thickness of the layered molded article means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated in the glass cloth or the like.
本実施形態に係る樹脂組成物から形成されるフィルム等の成形品は、 露光 現像してパターンを形成する用途に用いてもよいし、 露光現像しない用途に 用いてもよい。 特に、 露光現像しない用途に適している。 A molded product such as a film formed from the resin composition according to the present embodiment may be used for the purpose of exposing and developing to form a pattern, or may be used for the purpose of not exposing and developing. In particular, it is suitable for applications not exposed to light and developed.
[0072] «プリプレグ》 [0072] «Prepreg»
好ましい実施形態に係るプリプレグは、 基材 (プリプレグ基材) と、 本実 施形態に係る樹脂組成物とから形成される。 本実施形態のプリプレグは、 例 えば、 本実施形態に係る樹脂組成物を基材に適用 (例えば、 含浸または塗布 ) させた後、 加熱 (例えば、 1 2 0 ~ 2 2 0 °〇で2 ~ 1 5分乾燥させる方法 等) によって半硬化させることにより得られる。 この場合、 基材に対する樹 脂組成物の付着量、 すなわち半硬化後のプリプレグの総量に対する樹脂組成 物量 (充填材を含む) は、 2 0〜 9 9質量%の範囲であることが好ましい。 The prepreg according to the preferred embodiment is formed from a base material (prepreg base material) and the resin composition according to the present embodiment. In the prepreg of the present embodiment, for example, after the resin composition according to the present embodiment is applied (eg, impregnated or applied) to a base material, it is heated (eg, 120 to 220 °° C. for 2 to It is obtained by semi-curing by a method of drying for 15 minutes, etc.). In this case, the amount of the resin composition attached to the base material, that is, the amount of the resin composition (including the filler) with respect to the total amount of the prepreg after semi-curing is preferably in the range of 20 to 99% by mass.
[0073] 基材としては、 各種プリント配線板材料に用いられている基材であれば特 に限定されない。 基材の材質としては、 例えば、 ガラス繊維 (例えば、 巳ガ ラス、 ロガラス、 !_ガラス、 3ガラス、 丁ガラス、 〇ガラス、 11 1\1ガラス、 巳ガラス、 球状ガラス等) 、 ガラス以外の無機繊維 (例えば、 クォーツ等 ) 、 有機繊維 (例えば、 ポリイミ ド、 ポリアミ ド、 ポリエステル、 液晶ポリ エステル等) が挙げられる。 基材の形態としては、 特に限定されず、 織布、 不織布、 口ービング、 チョップドストランドマッ ト、 サーフエシングマッ ト 等の層状の繊維から構成される基材が挙げられる。 特に、 ガラスクロス等の 長繊維から構成される基材が好ましい。 ここで、 長繊維とは、 例えば、 数平 均繊維長が 6
以上のものをいう。 これらの基材は、 1種を単独で、 また
〇 2020/175537 33 卩(:171? 2020 /007686 [0073] The substrate is not particularly limited as long as it is a substrate used for various printed wiring board materials. Examples of the material for the base material include glass fiber (for example, glass, glass, ro glass, !_ glass, 3 glass, cho glass, glass, 11 1\1 glass, glass, spherical glass, etc.) and glass other than glass. Inorganic fibers (eg, quartz) and organic fibers (eg, polyimide, polyamide, polyester, liquid crystal polyester, etc.) can be mentioned. The form of the base material is not particularly limited, and examples thereof include a base material composed of layered fibers such as woven cloth, non-woven cloth, mouth roving, chopped strand mat, and surf essing mat. In particular, a substrate composed of long fibers such as glass cloth is preferable. Here, the long fiber means, for example, that the number average fiber length is 6 The above is said. These base materials may be used alone or 〇 2020/175 537 33 卩 (:171? 2020 /007686
は 2種以上を組み合わせて用いることができる。 これらの基材の中でも、 寸 法安定性の観点から、 超開繊処理、 目詰め処理を施した織布が好ましく、 吸 湿耐熱性の観点から、 エポキシシラン処理、 アミノシラン処理などのシラン カップリング剤等により表面処理したガラス織布が好ましく、 電気特性の観 点から、 1_ _ガラスや 巳_ガラス、 〇_ガラス等の低誘電率性、 低誘電正 接性を示すガラス繊維からなる、 低誘電ガラスクロスが好ましい。 基材の厚 みは、 特に限定されず、 例えば、 〇. 0 1〜 0 . 1
程度であってもよ い。 Can be used in combination of two or more kinds. Among these base materials, woven fabrics that have undergone super-opening treatment and filling treatment are preferable from the viewpoint of dimensional stability, and silane coupling such as epoxy silane treatment and amino silane treatment from the viewpoint of moisture absorption heat resistance. A glass woven fabric whose surface is treated with an agent is preferable, and from the viewpoint of electrical characteristics, it is made of glass fiber having low dielectric constant and low dielectric loss tangent such as 1_ _ glass, _ glass, and _ glass. Dielectric glass cloth is preferred. The thickness of the base material is not particularly limited, and may be, for example, 0.01 to 0.1. It may be a degree.
[0074] «金属箔張積層板》 [0074] «Metal foil-clad laminate»
好ましい実施形態に係る金属箔張積層板は、 本実施形態のプリプレグから 形成された少なくとも 1つの層と、 前記プリプレグから形成された層の片面 または両面に配置された金属箔とを含む。 本実施形態の金属箔張積層板は、 例えば、 本実施形態のプリプレグを少なくとも 1枚配置し (好ましくは 2枚 以上重ね) 、 その片面または両面に金属箔を配置して積層成形する方法で作 製できる。 より詳細には、 プリプレグの片面または両面に銅、 アルミニウム 等の金属箔を配置して積層成形することにより作製できる。 プリプレグの枚 数としては、 1〜 1 0枚が好ましく、 2〜 1 0枚がより好ましく、 2〜 7枚 がさらに好ましい。 金属箔としては、 プリント配線板用材料に用いられるも のであれば特に限定されないが、 例えば、 圧延銅箔、 電解銅箔等の銅箔が挙 げられる。 銅箔の厚さは、 特に限定されず、 1 . 5〜 7 0 程度であって もよい。 成形方法としては、 プリント配線板用積層板および多層板を成形す る際に通常用いられる方法が挙げられ、 より詳細には多段プレス機、 多段真 空プレス機、 連続成形機、 オートクレープ成形機等を使用して、 温度 1 8 0 〜 3 5 0 程度、 加熱時間 1 0 0〜 3 0 0分程度、
The metal foil-clad laminate according to a preferred embodiment includes at least one layer formed of the prepreg of the present embodiment and a metal foil arranged on one side or both sides of the layer formed of the prepreg. The metal foil-clad laminate of the present embodiment is produced, for example, by a method in which at least one prepreg of the present embodiment is arranged (preferably two or more prepregs), and a metal foil is arranged on one side or both sides of the prepreg to laminate-mold. Can be manufactured. More specifically, it can be produced by arranging a metal foil of copper, aluminum or the like on one or both sides of the prepreg and laminating and molding. The number of prepreg sheets is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 7 sheets. The metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foil such as rolled copper foil and electrolytic copper foil. The thickness of the copper foil is not particularly limited, and may be about 1.5 to 70. Examples of the molding method include methods commonly used for molding laminated boards and multilayer boards for printed wiring boards, and more specifically, multi-stage press machines, multi-stage vacuum press machines, continuous molding machines, autoclape molding machines. Etc., the temperature is about 180 ~ 350, the heating time is about 100 ~ 300 minutes,
〇〇! 2程度で積層成形する方法が挙げられる。 また、 本実施形態のプリプレグ と、 別途作製した内層用の配線板 (内層回路板ともいう) とを組み合わせて 積層成形することにより、 多層板とすることもできる。 多層板の製造方法と しては、 例えば、 本実施形態のプリプレグ 1枚の両面に 3 5 程度の銅箔
〇 2020/175537 34 卩(:171? 2020 /007686 And a method of laminate molding at about hundred! 2. Also, a multilayer board can be obtained by laminating and molding the prepreg of the present embodiment and a wiring board for an inner layer (also referred to as an inner layer circuit board) separately manufactured. Examples of the method for manufacturing a multilayer board include, for example, about 35 copper foils on both sides of one prepreg of this embodiment. 〇 2020/175 537 34 卩 (:171? 2020 /007686
を配置し、 上記の成形方法にて積層形成した後、 内層回路を形成し、 この回 路に黒化処理を実施して内層回路板を形成し、 この後、 この内層回路板と本 実施形態のプリプレグとを交互に 1枚ずつ配置し、 さらに最外層に銅箔を配 置して、 上記条件にて好ましくは真空下で積層成形することにより、 多層板 を作製することができる。 本実施形態の金属箔張積層板は、 プリント配線板 として好適に使用することができる。 After forming the inner layer circuit by the above-mentioned molding method, an inner layer circuit is formed, and blackening treatment is performed on this circuit to form an inner layer circuit board. By alternately arranging the above-mentioned prepregs one by one, further arranging a copper foil on the outermost layer, and laminating under the above conditions, preferably under vacuum, a multilayer board can be produced. The metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.
[0075] «プリント配線板» [0075] «Printed wiring board»
好ましい実施形態に係るプリント配線板は、 絶縁層と、 前記絶縁層の表面 に配置された導体層とを含むプリント配線板であって、 前記絶縁層が、 本実 施形態に係る樹脂組成物から形成された層および上記実施形態に係るプリプ レグから形成された層の少なくとも一方を含む。 このようなプリント配線板 は、 常法に従って製造でき、 その製造方法は特に限定されない。 以下、 プリ ント配線板の製造方法の一例を示す。 まず上述した銅箔張積層板等の金属箔 張積層板を用意する。 次に、 金属箔張積層板の表面にエッチング処理を施し て内層回路の形成を行い、 内層基板を作製する。 この内層基板の内層回路表 面に、 必要に応じて接着強度を高めるための表面処理を行い、 次いでその内 層回路表面に上述したプリプレグを所要枚数重ね、 さらにその外側に外層回 路用の金属箔を積層し、 加熱加圧して一体成形する。 このようにして、 内層 回路と外層回路用の金属箔との間に、 基材および熱硬化性樹脂組成物の硬化 物からなる絶縁層が形成された多層の積層板が製造される。 次いで、 この多 層の積層板にスルーホールやバイアホール用の穴あけ加工を施した後、 この 穴の壁面に内層回路と外層回路用の金属箔とを導通させるめっき金属皮膜を 形成し、 さらに外層回路用の金属箔にエッチング処理を施して外層回路を形 成することで、 プリント配線板が製造される。 A printed wiring board according to a preferred embodiment is a printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer, wherein the insulating layer is formed from the resin composition according to the present embodiment. At least one of the formed layer and the layer formed from the prepreg according to the above embodiment is included. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. An example of a method for manufacturing a printed wiring board will be shown below. First, a metal foil-clad laminate such as the copper foil-clad laminate described above is prepared. Next, the surface of the metal foil-clad laminate is subjected to an etching treatment to form an inner layer circuit, thereby manufacturing an inner layer substrate. If necessary, a surface treatment is performed on the surface of the inner layer circuit of this inner layer substrate to increase the adhesive strength, then the required number of the above-mentioned prepregs are layered on the inner layer circuit surface, and the outer layer metal for outer layer circuit is placed on the outer side. The foils are laminated and heated and pressed to integrally mold them. In this way, a multilayer laminate having an insulating layer made of a base material and a cured product of a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this multi-layer laminate, a plated metal film is formed on the wall surface of the holes to electrically connect the inner layer circuit and the metal foil for the outer layer circuit, and then the outer layer. A printed wiring board is manufactured by forming an outer layer circuit by etching a metal foil for a circuit.
[0076] 上記の製造例で得られるプリント配線板は、 絶縁層と、 この絶縁層の表面 に形成された導体層とを有し、 絶縁層が上述した本実施形態の樹脂組成物を 含む構成となる。 すなわち、 上述した本実施形態のプリプレグ (例えば、 基 材およびこれに含浸または塗布された本実施形態の樹脂組成物から形成され
〇 2020/175537 35 卩(:171? 2020 /007686 The printed wiring board obtained in the above Production Example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment described above. Becomes That is, the prepreg of the present embodiment described above (for example, formed from the base material and the resin composition of the present embodiment impregnated or applied thereto) 〇 2020/175 537 35 卩 (:171? 2020 /007686
たプリプレグ) 、 上述した本実施形態の金属箔張積層板の樹脂組成物から形 成された層が、 本実施形態の絶縁層となる。 Prepreg), and the layer formed from the resin composition of the metal foil-clad laminate of the present embodiment described above serves as the insulating layer of the present embodiment.
[0077] «樹脂複合シート》 [0077] «Resin composite sheet»
好ましい実施形態に係る樹脂複合シートは、 支持体と、 前記支持体の表面 に配置された本実施形態に係る樹脂組成物から形成された層とを含む。 樹脂 複合シートは、 ビルドアップ用フィルムまたはドライフィルムソルダーレジ ストとして使用することができる。 樹脂複合シートの製造方法としては、 特 に限定されないが、 例えば、 上記の本実施形態の樹脂組成物を溶剤に溶解さ せた溶液を支持体に塗布 (塗工) し乾燥することで樹脂複合シートを得る方 法が挙げられる。 The resin composite sheet according to a preferred embodiment includes a support and a layer formed on the surface of the support and formed from the resin composition according to the present embodiment. The resin composite sheet can be used as a build-up film or a dry film solder resist. The method for producing the resin composite sheet is not particularly limited. For example, a solution obtained by dissolving the resin composition of the present embodiment described above in a solvent is applied to a support (coating) and dried to obtain a resin composite sheet. One method is to obtain a seat.
[0078] ここで用いる支持体としては、 例えば、 ポリエチレンフィルム、 ポリプロ ピレンフィルム、 ポリカーボネートフィルム、 ポリエチレンテレフタレート フィルム、 エチレンテトラフルオロエチレン共重合体フィルム、 並びにこれ らのフィルムの表面に離型剤を塗布した離型フィルム、 ポリイミ ドフィルム 等の有機系のフィルム基材、 銅箔、 アルミ箔等の導体箔、 ガラス板、 3 11 3 板、
等の板状のものが挙げられるが、 特に限定されるものではない。 [0078] Examples of the support used here include a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a release agent applied on the surface of these films. Release film, organic film substrate such as polyimide film, conductor foil such as copper foil and aluminum foil, glass plate, 3 11 3 plate, Examples thereof include plate-shaped ones, but are not particularly limited.
[0079] 塗布方法 (塗工方法) としては、 例えば、 樹脂組成物を溶剤に溶解させた 溶液を、 バーコーター、 ダイコーター、 ドクターブレード、 ベーカーアプリ ケーター等で支持体上に塗布する方法が挙げられる。 また、 乾燥後に、 支持 体と樹脂組成物が積層された樹脂複合シートから支持体を剥離またはエッチ ングすることで、 単層シートとすることもできる。 なお、 上記の本実施形態 の樹脂組成物を溶剤に溶解させた溶液を、 シート状のキャビティを有する金 型内に供給し乾燥する等してシート状に成形することで、 支持体を用いるこ となく単層シートを得ることもできる。 [0079] Examples of the coating method (coating method) include a method in which a solution prepared by dissolving a resin composition in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator or the like. To be Further, after drying, the support may be peeled off or etched from the resin composite sheet in which the support and the resin composition are laminated to obtain a single-layer sheet. The support can be used by forming a sheet by supplying the solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-like cavity and drying it. It is also possible to obtain a single layer sheet.
[0080] 本実施形態の樹脂複合シートの作製において、 溶剤を除去する際の乾燥条 件は、 特に限定されないが、 低温であると樹脂組成物中に溶剤が残りやすく 、 高温であると樹脂組成物の硬化が進行することから、 2 0 °〇〜 2 0 0 °〇の 温度で 1〜 9 0分間が好ましい。 また、 樹脂複合シートにおいて、 樹脂組成
〇 2020/175537 36 卩(:171? 2020 /007686 In the production of the resin composite sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but the solvent tends to remain in the resin composition at low temperature, and the resin composition at high temperature. since the curing of the object progresses, preferably 2 0 ° 〇_~ 2 0 0 ° at 〇 temperature 1-9 0 min. In the resin composite sheet, the resin composition 〇 2020/175 537 36 卩 (:171? 2020 /007686
物は溶剤を乾燥しただけの未硬化の状態で使用することもできるし、 必要に 応じて半硬化 (巳ステージ化) の状態にして使用することもできる。 さらに 、 本実施形態の樹脂複合シートの樹脂層の厚みは、 本実施形態の樹脂組成物 の溶液の濃度と塗布厚みにより調整することができ、 特に限定されないが、 一般的には塗布厚みが厚くなると乾燥時に溶剤が残りやすくなることから、 〇. 1〜 5 0 0 が好ましい。 The product can be used in an uncured state by just drying the solvent, or can be used in a semi-cured (staged) state if necessary. Further, the thickness of the resin layer of the resin composite sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited, but generally the coating thickness is large. If so, the solvent is likely to remain during drying, so that the range of 0.1 to 500 is preferable.
実施例 Example
[0081 ] 以下に実施例を挙げて本発明をさらに具体的に説明する。 以下の実施例に 示す材料、 使用量、 割合、 処理内容、 処理手順等は、 本発明の趣旨を逸脱し ない限り、 適宜、 変更することができる。 従って、 本発明の範囲は以下に示 す具体例に限定されるものではない。 [0081] The present invention will be described more specifically with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
本実施例において、 特に述べない限り、 測定は 2 3 °〇で行った。 In this example, unless otherwise stated, the measurement was performed at 23 ° .
[0082] <実施例 1 > [0082] <Example 1>
下記で合成した多官能ビニルベンゼン重合体 (3 ) 7 5質量部と、 ビフ エニルアラルキル型マレイミ ド (日本化薬社製、 1\/1 丨 [¾ - 3 0 0 0 (商品名 ) ) 2 5質量部と、 イミダゾール触媒 (四国化成社製、 2巳4 !\/1 2 (商品名 ) ) 0 . 5質量部とを、 メチルエチルケトンで溶解して混合し、 ワニスを得 た。 75 parts by mass of the polyfunctional vinylbenzene polymer (3) synthesized below, and biphenylaralkyl-type maleimide (manufactured by Nippon Kayaku Co., Ltd., 1\/1丨 [¾-300 0 (trade name)) 2 5 parts by mass and 0.5 parts by mass of an imidazole catalyst (manufactured by Shikoku Kasei Co., Ltd., 2m 4 !\/ 12 (trade name)) were dissolved and mixed with methyl ethyl ketone to obtain a varnish.
[0083] (多官能ビニルベンゼン重合体 (3 ) の合成) [0083] (Synthesis of polyfunctional vinylbenzene polymer (3))
ジビニルベンゼン 2 . 2 5モル (2 9 2 . 9 ) 、 エチルビニルベンゼン 1 . 3 2モル ( 1 7 2 . 0 ) 、 スチレン 1 1 . 4 3モル ( 1 1 9 0 . 3 9 ) 、 酢酸 11 -プロピル 1 5 . 0モル (1 5 3 2 . 0 9) を反応器内に投入し 、 7 0 °〇で 6 0 0ミリモルの三フッ化ホウ素のジエチルエーテル錯体を添加 し、 4時間反応させた。 重合溶液を炭酸水素ナトリウム水溶液で停止させた 後、 純水で 3回油層を洗浄し、 6 0 °〇で減圧脱揮し、 多官能ビニルベンゼン 重合体 (3 ) を回収した。 得られた多官能ビニルベンゼン重合体 (3 ) を秤量して、 多官能ビニルベンゼン重合体 (3 ) 8 6 0 . 8 9が得られた ことを確認した。
〇 2020/175537 37 卩(:171? 2020 /007686 Divinylbenzene 2 .25 mol (2 92.9), ethylvinylbenzene 1 .3 2 mol (1 72.0), styrene 1 1 .4 3 mol (1 1 10.9 0.39), acetic acid 11 -Propyl 15.0 mol (153 32.0 9 ) was charged into the reactor, and 600 mmol of diethyl ether complex of boron trifluoride was added at 70 ° and reacted for 4 hours. It was After stopping the polymerization solution with an aqueous solution of sodium hydrogen carbonate, the oil layer was washed with pure water three times and degassed under reduced pressure at 60 ° to recover a polyfunctional vinylbenzene polymer (3). The obtained polyfunctional vinylbenzene polymer (3) was weighed, and it was confirmed that the polyfunctional vinylbenzene polymer (3) 860.89 was obtained. 〇 2020/175 537 37 卩 (:171? 2020 /007686
[0084] 得られた多官能ビニルベンゼン重合体 (3 ) のMnは 2060、
[0084] The Mn of the obtained polyfunctional vinylbenzene polymer (3) was 2060,
30700、
9であった。 13〇 - IV! および 11~1 - IV! 8分析を行うことにより、 多官能ビニルベンゼン重合体 (3 ) には、 各単 量体単位に由来する共鳴線が観察された。
測定結果、 および、 ◦〇分 析結果に基づき、 多官能ビニルベンゼン重合体 (3 ) の構成単位の割合は 以下のように算出された。 30700, Was 9. By conducting 13 0 -IV! and 11 ~ 1 -IV! 8 analyzes, resonance lines derived from each monomer unit were observed in the polyfunctional vinylbenzene polymer (3). Based on the measurement results and the ◯ analysis results, the ratio of the constituent units of the polyfunctional vinylbenzene polymer (3) was calculated as follows.
ジビニルベンゼン由来の構成単位: 2〇. 9モル% (24. 3質量%) エチルビニルベンゼン由来の構成単位: 9. 1モル%(1 0. 7質量%) スチレンに由来する構成単位: 70. 0モル% (65. 0質量%) Structural units derived from divinylbenzene: 209 mol% (24.3% by mass) Structural units derived from ethylvinylbenzene: 9.1 mol% (10.7% by mass) Structural units derived from styrene: 70. 0 mol% (65.0 mass%)
また、 ジビニルベンゼン由来の残存ビニル基をもつ構成単位は、 1 6. 7 モル% (1 8. 5質量%) であった。 The constitutional unit having a residual vinyl group derived from divinylbenzene was 16.7 mol% (18.5% by mass).
[0085] «厚さ 1. 6 〇!の硬化板の試験片の製造》 [0085] «Manufacture of test pieces of cured plate with a thickness of 1.60!
得られたワニスから溶剤を蒸発留去することで混合樹脂粉末を得た。 混合 樹脂粉末を 1辺 1 00〇!〇!、 厚さ 1. 60101の型に充填し、 両面に 1 2 銅箔 (3巳(3-1\/13- 1_ ?、 三井金属鉱業 (株) 製) を配置し、 圧力 30 1< 9/〇〇12、 温度 220°〇で 1 20分間真空プレスを行い、
A solvent was evaporated from the obtained varnish to obtain a mixed resin powder. The mixed resin powder is filled in a mold with a side of 100 〇! 〇! and a thickness of 1.60101, and 1 2 copper foil (3M (3-1\/13-1_?, Mitsui Mining & Smelting Co., Ltd.) Ltd.) were placed, pressure 30 1 <9 / Rei_rei_1 2 and vacuum press 1 for 20 minutes at a temperature 220 ° 〇,
[0086] 得られた 1. 6 厚の硬化板について、 後述する方法に従って物性等 ( 誘電特性 (〇 !<、 0†) 、 ピール強度、 ガラス転移温度、 熱膨張係数 (<3丁 º) ) の評価を行った。 With respect to the obtained 1.6-thick cured plate, the physical properties and the like (dielectric properties (〇 !<, 0†), peel strength, glass transition temperature, coefficient of thermal expansion (<3°)) were measured according to the method described later. Was evaluated.
[0087] <実施例 2> <Example 2>
ビフエニルアラルキル型マレイミ ド 25質量部を 1 2. 5質量部とし、 フ エニルエーテル型マレイミ ド (ケイ · アイ化成社製、 巳1\/1 丨 -80 (商品名) 25 parts by weight of biphenyl aralkyl type maleimide is set to 12.5 parts by weight, and a phenyl ether type maleimide (manufactured by K.I Kasei Co., Ltd., 1 1//1 -80 (trade name))
) 1 2. 5質量部を追加した以外は、 実施例 1 と同様にして、 ワニスを得た 。 得られたワニスより、 実施例 1 と同様にして、 1.
厚の硬化板を得 た。 得られた 1. 6
厚の硬化板について、 後述する方法に従って物性等 の評価を行った。 1) A varnish was obtained in the same manner as in Example 1 except that 12.5 parts by mass was added. From the obtained varnish, in the same manner as in Example 1, 1. A thick cured plate was obtained. Obtained 1.6 The thick cured plate was evaluated for physical properties and the like according to the methods described below.
[0088] <実施例 3>
〇 2020/175537 38 卩(:171? 2020 /007686 [0088] <Example 3> 〇 2020/175 537 38 卩 (:171? 2020 /007686
ビフエニルアラルキル型マレイミ ド 25質量部に代えて、 巳 丨 3 IV!型マレ イミ ド (ケイ · アイ化成社製、 巳1\/1 I -巳 丨
(商品名) ) 25質量部を用 いた以外実施例 1 と同様にして、 ワニスを得た。 得られたワニスより、 実施 例 1 と同様にして、 1. 6
厚の硬化板を得た。 得られた 1.
硬化板について、 後述する方法に従って物性等の評価を行った。 In place of 25 parts by weight of biphenyl aralkyl type maleide, 巳丨 3 IV! type maleimide (Ki I Kasei Co., Ltd., 1 1//1 I-巳 丨 (Brand name) A varnish was obtained in the same manner as in Example 1 except that 25 parts by mass was used. From the obtained varnish, in the same manner as in Example 1, 1.6 A thick cured plate was obtained. Obtained 1. The cured plate was evaluated for physical properties and the like according to the methods described below.
[0089] <実施例 4> [0089] <Example 4>
ビフエニルアラルキル型マレイミ ド 25質量部に代えて、 末端変成ポリフ エニレンエーテル (三菱ガス化学社製、 〇 巳一23 1 200 (商品名 ) ) 25質量部を用い、 イミダゾール触媒を用いなかった以外は、 実施例 1 と同様にして、 ワニスを得た。 得られたワニスより、 実施例 1 と同様にして 、 1. 6
厚の硬化板を得た。 得られた 1.
厚の硬化板について、 後述する方法に従って物性等の評価を行った。 In place of 25 parts by mass of biphenyl aralkyl type maleimide, 25 parts by mass of end-modified polyphenylene ether (manufactured by Mitsubishi Gas Chemical Co., Ltd., 巳一 23 1 200 (trade name)) was used, and no imidazole catalyst was used. A varnish was obtained in the same manner as in Example 1. From the obtained varnish, in the same manner as in Example 1, 1.6 A thick cured plate was obtained. Obtained 1. The thick cured plate was evaluated for physical properties and the like according to the methods described below.
[0090] <実施例 5> [0090] <Example 5>
ビフエニルアラルキル型マレイミ ド 25質量部に代えて、 下記のナフトー ルアラルキル型シアン酸エステル樹脂 25質量部を用い、 イミダゾール触媒 〇. 5質量部に代えて、 有機金属触媒 (日本化学産業社製、
(商 品名) ) 〇. 1質量部を用いた以外は、 実施例 1 と同様にして、 ワニスを得 た。 得られたワニスより、 実施例 1 と同様にして、 1.
厚の硬化板を 得た。 得られた 1.
厚の硬化板について、 後述する方法に従って物性 等の評価を行った。 25 parts by mass of the following naphthol aralkyl type cyanate ester resin was used in place of 25 parts by mass of the biphenyl aralkyl type maleimide, and an organometallic catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., in place of 0.5 parts by mass of the imidazole catalyst) was used. (Commercial name) ○ A varnish was obtained in the same manner as in Example 1 except that 0.1 part by mass was used. From the obtained varnish, in the same manner as in Example 1, 1. A thick cured plate was obtained. Obtained 1. The thick cured plate was evaluated for physical properties according to the methods described below.
[0091] («_ナフトールアラルキル型シアン酸エステル樹脂の合成) [0091] («_ Synthesis of naphthol aralkyl type cyanate ester resin)
トールアラルキル樹脂 (3 495 V、 〇 1~1基当量: 2369 / 69. 、 新日鐵化学 (株) 製:ナフトールアラルキルの繰り返し単位数は 1 〜 5のものが含まれる。 ) 〇. 47モル (〇1~1基換算) を、 クロロホルム 5 00 !_に溶解させ、 この溶液にトリエチルアミン〇. 7モルを添加し、 溶 液 1 を作成した。 温度を一 1 〇°〇に保ちながら、 反応器内に仕込んだ 0. 9 3モルの塩化シアンのクロロホルム溶液 3009に、 溶液 1 を 1. 5時間か けて滴下し、 滴下終了後、 30分撹拌した。 その後、 さらに、 〇. 1モルの
〇 2020/175537 39 卩(:171? 2020 /007686 Tall aralkyl resin (3 495 V, 0 to 1 base equivalent: 2369 / 69., manufactured by Nippon Steel Chemical Co., Ltd.: naphthol aralkyl has 1 to 5 repeating units.) 〇.47 mol the (Rei_1 ~ 1 group basis), chloroform 5 00! dissolved in _, the solution was added triethylamine 〇. 7 mol to prepare a dissolved solution 1. While keeping the temperature at 110 ° C, Solution 1 was added dropwise to 0.93 mol of cyanogen chloride in chloroform solution 3009 charged in the reactor over 1.5 hours, and 30 minutes after the addition was completed. It was stirred. Then, in addition, 0.1 mol 〇 2020/175 537 39 卩 (:171? 2020 /007686
トリエチルアミンとクロロホルム 3 0 9の混合溶液を反応器内に滴下し、 3 〇分撹拌して反応を完結させた。 副生したトリエチルアミンの塩酸塩を反応 液から濾別した後、 得られた濾液を〇. 1 1\1塩酸 5 0 0 1_で洗浄した後、 水 5 0 0 1_での洗浄を 4回繰り返した。 これを硫酸ナトリウムにより乾燥 した後、 7 5 °〇でエバポレートし、 さらに 9 0 °〇で減圧脱気することにより 、 褐色固形の式 (3 1) で表される ナフトールアラルキル型シアン酸エ ステル化合物 (式中の
はすべて水素原子であり、 门。は1 ~ 5の混 合物である。 ) を得た。 得られた ナフトールアラルキル型シアン酸エス テル化合物を赤外吸収スぺクトルにより分析したところ、 2 2 6 4〇
付 近にシアン酸エステル基の吸収が確認された。 A mixed solution of triethylamine and chloroform 309 was dropped into the reactor and stirred for 30 minutes to complete the reaction. After the triethylamine hydrochloride by-produced was filtered out from the reaction solution, the obtained filtrate was washed with 0. 1 1\1 hydrochloric acid 5 0 0 1_ and then with water 5 0 0 1_ 4 times. I repeated. After drying over sodium sulfate, it was evaporated at 75° and degassed under reduced pressure at 90° to give a brown solid naphthol aralkyl-type cyanate ester compound of the formula (3 1). (In the formula Are all hydrogen atoms, Is a mixture of 1 to 5. ) Got The obtained naphthol aralkyl-type cyanate ester compound was analyzed by infrared absorption spectrum. In the vicinity, absorption of cyanate ester group was confirmed.
[化 22] [Chemical 22]
[0092] <参考例 1 > [0092] <Reference example 1>
熱ラジカル重合開始剤 (日油社製、 パープチル (商品名) ) 1質量 部を追加した以外は、 実施例 1 と同様にして、 ワニスを得た。 得られたワニ スより、 実施例 1 と同様にして、 1 .
厚の硬化板を得た。 得られた 1 . 厚の硬化板について、 後述する方法に従って物性等の評価を行った A varnish was obtained in the same manner as in Example 1 except that 1 part by mass of a thermal radical polymerization initiator (Palptyl (trade name) manufactured by NOF CORPORATION) was added. From the obtained varnish, in the same manner as in Example 1, 1. A thick cured plate was obtained. With respect to the obtained 1-thick cured plate, physical properties and the like were evaluated according to the methods described below.
[0093] <参考例 2 > [0093] <Reference example 2>
熱ラジカル重合開始剤 (日油社製、 パープチル (商品名) ) 1質量 部を追加した以外は、 実施例 4と同様にして、 ワニスを得た。 得られたワニ スより、 実施例 4と同様にして、 1 .
厚の硬化板を得た。 得られた 1 . 厚の硬化板について、 後述する方法に従って物性等の評価を行った A varnish was obtained in the same manner as in Example 4 except that 1 part by mass of a thermal radical polymerization initiator (Palptyl (trade name) manufactured by NOF CORPORATION) was added. From the obtained varnish, in the same manner as in Example 4, 1. A thick cured plate was obtained. With respect to the obtained 1-thick cured plate, physical properties and the like were evaluated according to the methods described below.
[0094] <参考例 3 >
熱ラジカル重合開始剤 (日油社製、 パープチル P (商品名) ) 1質量 部を追加した以外は、 実施例 5と同様にして、 ワニスを得た。 得られたワニ スより、 実施例 5と同様にして、 1. 6 mm厚の硬化板を得た。 得られた 1 . 6 m m厚の硬化板について、 後述する方法に従って物性等の評価を行った [0094] <Reference example 3> A varnish was obtained in the same manner as in Example 5, except that 1 part by mass of a thermal radical polymerization initiator (Palpyl P (trade name) manufactured by NOF CORPORATION) was added. A 1.6 mm thick cured plate was obtained from the obtained varnish in the same manner as in Example 5. The obtained 1.6 mm-thick cured plate was evaluated for physical properties according to the methods described below.
[0095] <誘電特性 (D kおよび D f ) > [0095] <Dielectric Properties (D k and D f )>
得られた 1. 6 mm厚の硬化板の銅箔をエッチングにより除去した試験片 について、 摂動法空洞共振器を用いて、 1 0GH zにおける比誘電率 (D k ) および誘電正接 (D f ) を測定した。 測定温度は 23 °Cとした。 Using the perturbation method cavity resonator, the dielectric constant (D k) and dielectric loss tangent (D f) at 10 GHz of the obtained test piece from which the copper foil of the 1.6 mm thick cured plate was removed by etching were used. Was measured. The measurement temperature was 23 ° C.
摂動法空洞共振器は、 アジレントテクノロジー社製品、 A g i I e n t 8 722 E Sを用いた。 As the perturbation method cavity resonator, Aggi Ie n t 8 722 E S, a product of Agilent Technologies, Inc. was used.
[0096] <ピ_ル強度> [0096] <Peel strength>
上記のようにして得られた硬化板を用い、 J I S C6481の 5. 7 「引きはがし強さ」 の規定に準じて、 銅箔ピール強度 (接着力) を 2回測定 し、 平均値を求めた。 測定温度は 23°Cとした。 Using the cured plate obtained as described above, the copper foil peel strength (adhesive strength) was measured twice in accordance with JIS C6481 5.7 “Peeling strength”, and the average value was obtained. .. The measurement temperature was 23 ° C.
[0097] <ガラス転移温度> <Glass transition temperature>
ガラス転移温度 (T g) は、 得られた 1. 6 mm厚の硬化板の銅箔をエッ チングにより除去した試験片について、 J I S C 6481 5. 1 7. 2 に準拠して、 動的粘弾性分析装置で DM A (動的機械分析: D y n a m i c Me c h a n i c a l A n a l y s i s) 曲げ法により測定した。 得ら れた t a n 5のチヤートからガラス転移温度を見積もった。 The glass transition temperature (T g) of the test piece obtained by removing the copper foil of the obtained 1.6 mm thick cured plate by etching is in accordance with JIS C 6481 5. 1 7. 2 It was measured by a DMA (Dynamic Mechanical Analysis) bending method with an analyzer. The glass transition temperature was estimated from the obtained chart of t a n 5.
動的粘弾性分析装置は、 T Aインスツルメント製の装置を用いた。 As the dynamic viscoelasticity analyzer, an instrument manufactured by TA Instruments was used.
[0098] <熱膨張係数 (CT E) > [0098] <Thermal expansion coefficient (CT E)>
(C r t : Coefficient of linear Thermal Expansion) (Crt: Coefficient of linear Thermal Expansion)
1. 6 mm厚の硬化板の銅箔をエッチングにより除去した試験片に対し、 For the test piece from which the copper foil of the 1.6 mm thick cured plate was removed by etching,
J I S C 6481 5. 1 9 に規定される T M A法 (熱機械分析: T h e r mo— Me e h a n i c a l A n a l y s i s) により硬化板の熱 膨張係数を測定し、 その値を求めた。 具体的には、 上記で得られた硬化板の
〇 2020/175537 41 卩(:171? 2020 /007686 The coefficient of thermal expansion of the cured plate was measured by the TMA method (Thermo-Mechanical Analysis) specified in JIS C 6481 5.19, and the value was obtained. Specifically, of the cured plate obtained above 〇 2020/175 537 41 卩(: 171-1? 2020/007686
両面の銅箔をエッチングにより除去した後に、 熱機械分析装置 (丁 インス ツルメント製) で 40°〇から 340°〇まで毎分 1 0°〇で昇温し、 線熱膨張係 数 ( 01/°〇) を測定した。 01は、 体積比である。 その他の詳細につ いては、 上記」 丨 3 〇 6481 5. 1 9に準拠する。 Both sides of the copper foil was removed by etching, thermal mechanical analyzer (Ding Ltd. Instruments Tsurumento) with heated per minute 1 0 ° 〇 from 40 ° 〇 to 340 ° 〇, linear thermal expansion coefficient (01 / ° ◯) was measured. 01 is the volume ratio. For the other details, refer to the above “3 0 6481 5.19.
[0099]
[0099]
〔¾二 [¾ji
〇 2020/175537 43 卩(:171? 2020 /007686 〇 2020/175 537 43 卩 (:171? 2020 /007686
(表の注記) (Note in table)
0 1< : 1 0◦ 1~1 2における比誘電率 0 1<: 1 0 ◦ Relative permittivity between 1 and 12
ピール強度:銅箔の剥離試験の結果 Peel strength: Results of copper foil peel test
ガラス転移温度: 口1\/1八法により測定される 1 3 n 5から見積もられたガラ ス転移温度 Glass transition temperature: Glass transition temperature estimated from 1 3 n 5 measured by mouth 1\/1 method
〇丁巳 : 丁1\/1 法により測定された熱膨張係数 〇Chomi: Coefficient of thermal expansion measured by the Ding 1\/1 method
[0100] 上記表 1の結果から、 本実施形態に係る多官能ビニル芳香族重合体 (八) (多官能ビニルベンゼン重合体 (3 ) ) と熱硬化性化合物 (巳) とを組み 合わせた樹脂組成物は、 誘電特性 (低誘電率、 低誘電正接) に優れ、 かつ、 高いガラス転移温度および低熱膨張係数を有していた。 さらに、 ピール強度 も高かった。 [0100] From the results in Table 1 above, a resin obtained by combining the polyfunctional vinyl aromatic polymer (8) according to the present embodiment (polyfunctional vinylbenzene polymer (3)) and the thermosetting compound (Mitsumi) The composition was excellent in dielectric properties (low dielectric constant, low dielectric loss tangent), and had a high glass transition temperature and a low thermal expansion coefficient. Furthermore, the peel strength was also high.
一方、 ラジカル重合開始剤を含有すると、 参考例 1 と実施例 1、 参考例 2 と実施例 4、 参考例 3と実施例 5との対比から明らかなとおり、 誘電正接が 高くなり、 ガラス転移温度が低下し、 熱膨張係数も高くなった。 さらに、 ピ _ル強度も低かった。
On the other hand, when the radical polymerization initiator is contained, the dielectric loss tangent is increased and the glass transition temperature is increased as is clear from the comparison between Reference Example 1 and Example 1, Reference Example 2 and Example 4, and Reference Example 3 and Example 5. Decreased, and the coefficient of thermal expansion also increased. Furthermore, the peel strength was also low.
Claims
[請求項 1 ] 多官能ビニル芳香族重合体 ( ) と熱硬化性化合物 (巳) とを含み 、 ラジカル重合開始剤を含まない樹脂組成物。 [Claim 1] A resin composition containing a polyfunctional vinyl aromatic polymer () and a thermosetting compound (M), and containing no radical polymerization initiator.
[請求項 2] 前記多官能ビニル芳香族重合体 ( ) が、 式 (V) で表される構成 単位を有する重合体である、 請求項 1 に記載の樹脂組成物。 2. The resin composition according to claim 1, wherein the polyfunctional vinyl aromatic polymer () is a polymer having a structural unit represented by the formula (V).
[化 1 ] [Chemical 1]
[請求項 3] 前記熱硬化性化合物 (巳) がシアナト基、 ビニル基、 マレイミ ド基 、 およびナジイミ ド基からなる群より選ばれる 1つ以上の官能基を有 する、 請求項 1 または 2に記載の樹脂組成物。 [Claim 3] The thermosetting compound (M) has at least one functional group selected from the group consisting of a cyanato group, a vinyl group, a maleimide group, and a nadiimide group. The resin composition described.
[請求項 4] 樹脂組成物中の樹脂成分の総量 1 〇〇質量部に対する、 前記熱硬化 性化合物 (巳) の含有量が、 5〜 9 5質量部である、 請求項 1〜 3の いずれか 1項に記載の樹脂組成物。 [Claim 4] The content of the thermosetting compound (Mimi) is 5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition, any one of claims 1 to 3. The resin composition according to Item 1.
[請求項 5] 樹脂組成物中の樹脂成分の総量 1 〇〇質量部に対する、 前記多官能 ビニル芳香族重合体 ( ) の含有量が、 5〜 9 5質量部である、 請求 項 1〜 4のいずれか 1項に記載の樹脂組成物。 [Claim 5] The content of the polyfunctional vinyl aromatic polymer () is 5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. The resin composition according to any one of 1.
[請求項 6] さらに充填材 (〇) を含む、 請求項 1〜 5のいずれか 1項に記載の 樹脂組成物。 [Claim 6] The resin composition according to any one of claims 1 to 5, further comprising a filler (○).
[請求項 7] 樹脂組成物中の樹脂成分の総量 1 〇〇質量部に対する、 前記充填材 (〇) の含有量が、 1 〇〜 5 0 0質量部である、 請求項 6に記載の樹 脂組成物。 [Claim 7] The resin according to claim 6, wherein the content of the filler (◯) is 100 to 500 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition. Fat composition.
[請求項 8] 基材と、 請求項 1〜 7のいずれか 1項に記載の樹脂組成物とから形 成された、 プリプレグ。
〇 2020/175537 45 卩(:171? 2020 /007686 [Claim 8] A prepreg formed from a base material and the resin composition according to any one of claims 1 to 7. 〇 2020/175 537 45 卩 (:171? 2020 /007686
[請求項 9] 請求項 8に記載のプリプレグから形成された少なくとも 1つの層と[Claim 9] At least one layer formed from the prepreg according to claim 8.
、 前記プリプレグから形成された層の片面または両面に配置された金 属箔とを含む、 金属箔張積層板。 A metal foil-clad laminate comprising a metal foil arranged on one side or both sides of a layer formed from the prepreg.
[請求項 10] 支持体と、 前記支持体の表面に配置された請求項 1〜 7のいずれか [Claim 10] A support, and any one of claims 1 to 7 arranged on the surface of the support.
1項に記載の樹脂組成物から形成された層とを含む、 樹脂複合シート A resin composite sheet, comprising a layer formed from the resin composition according to item 1.
[請求項 1 1 ] 絶縁層と、 前記絶縁層の表面に配置された導体層とを含むプリント 配線板であって、 前記絶縁層が、 請求項 1〜 7のいずれか 1項に記載 の樹脂組成物から形成された層および請求項 8に記載のプリプレグか ら形成された層の少なくとも一方を含む、 プリント配線板。
[Claim 11] A printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer, wherein the insulating layer is the resin according to any one of claims 1 to 7. A printed wiring board comprising at least one of a layer formed from the composition and a layer formed from the prepreg according to claim 8.
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KR1020217028419A KR20210133230A (en) | 2019-02-28 | 2020-02-26 | Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board |
CN202080016923.XA CN113490715A (en) | 2019-02-28 | 2020-02-26 | Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board |
JP2021502311A JP7409369B2 (en) | 2019-02-28 | 2020-02-26 | Resin compositions, prepregs, metal foil laminates, resin composite sheets, and printed wiring boards |
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KR (1) | KR20210133230A (en) |
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JP2019194307A (en) * | 2018-04-27 | 2019-11-07 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
KR20220134473A (en) | 2021-03-26 | 2022-10-05 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Polyimide, resin composition, resin film, laminate, coverlay film, copper foil with resin, metal-clad laminate plate and circuit board |
WO2023026829A1 (en) | 2021-08-25 | 2023-03-02 | 三菱瓦斯化学株式会社 | Resin composition, cured object, prepreg, metal-foil-clad laminate, resin sheet, and printed wiring board |
WO2023047783A1 (en) * | 2021-09-27 | 2023-03-30 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminated sheet, composite resin sheet, printed wiring board, and semiconductor device |
JPWO2023047782A1 (en) * | 2021-09-27 | 2023-03-30 | ||
WO2023171554A1 (en) * | 2022-03-11 | 2023-09-14 | 三菱瓦斯化学株式会社 | Resin composition, cured product, prepreg, metal-foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device |
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KR20220134473A (en) | 2021-03-26 | 2022-10-05 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Polyimide, resin composition, resin film, laminate, coverlay film, copper foil with resin, metal-clad laminate plate and circuit board |
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JP7409369B2 (en) | 2024-01-09 |
CN113490715A (en) | 2021-10-08 |
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