JP2018070564A - Vinylbenzylated phenol compound, method for producing the vinylbenzylated phenol compound, active ester resin, method for producing the active ester resin, thermosetting resin composition, cured product of the thermosetting resin composition, interlayer insulation material, prepreg, and method for producing prepreg - Google Patents
Vinylbenzylated phenol compound, method for producing the vinylbenzylated phenol compound, active ester resin, method for producing the active ester resin, thermosetting resin composition, cured product of the thermosetting resin composition, interlayer insulation material, prepreg, and method for producing prepreg Download PDFInfo
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- JP2018070564A JP2018070564A JP2016216213A JP2016216213A JP2018070564A JP 2018070564 A JP2018070564 A JP 2018070564A JP 2016216213 A JP2016216213 A JP 2016216213A JP 2016216213 A JP2016216213 A JP 2016216213A JP 2018070564 A JP2018070564 A JP 2018070564A
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- general formula
- group
- phenol compound
- resin composition
- thermosetting resin
- Prior art date
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- -1 phenol compound Chemical class 0.000 title claims abstract description 107
- 229920005989 resin Polymers 0.000 title claims abstract description 75
- 239000011347 resin Substances 0.000 title claims abstract description 75
- 150000002148 esters Chemical class 0.000 title claims abstract description 63
- 239000011342 resin composition Substances 0.000 title claims abstract description 58
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000011229 interlayer Substances 0.000 title claims description 13
- 239000012774 insulation material Substances 0.000 title description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 32
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 16
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 28
- 229920000647 polyepoxide Polymers 0.000 claims description 27
- 239000003822 epoxy resin Substances 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011810 insulating material Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- 239000012779 reinforcing material Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 56
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 229960001545 hydrotalcite Drugs 0.000 description 22
- 229910001701 hydrotalcite Inorganic materials 0.000 description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 238000000434 field desorption mass spectrometry Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- ZPANWZBSGMDWON-UHFFFAOYSA-N 1-[(2-hydroxynaphthalen-1-yl)methyl]naphthalen-2-ol Chemical compound C1=CC=C2C(CC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 ZPANWZBSGMDWON-UHFFFAOYSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 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
- 238000005574 benzylation reaction Methods 0.000 description 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
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- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
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- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
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- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
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- 150000001721 carbon Chemical group 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
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- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
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- 239000010440 gypsum Substances 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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Abstract
Description
本発明は、熱硬化性樹脂組成物の成分として有用な活性エステル樹脂、その活性エステル樹脂の製造方法、その活性エステル樹脂を製造するための原料の1種であるビニルベンジル化フェノール化合物、そのビニルベンジル化フェノール化合物の製造方法、上記の活性エステル樹脂を含有する熱硬化性樹脂組成物、当該熱硬化性樹脂組成物の硬化物、当該熱硬化性樹脂組成物を用いてなる層間絶縁材料、当該熱硬化性樹脂組成物を用いてなるプリプレグ、および当該プリプレグの製造方法に関する。 The present invention relates to an active ester resin useful as a component of a thermosetting resin composition, a method for producing the active ester resin, a vinylbenzylated phenol compound which is one of raw materials for producing the active ester resin, and vinyl Method for producing benzylated phenol compound, thermosetting resin composition containing active ester resin as described above, cured product of thermosetting resin composition, interlayer insulating material formed using thermosetting resin composition, The present invention relates to a prepreg using a thermosetting resin composition and a method for producing the prepreg.
近年の情報通信機器の高機能化、高密度化などの性能向上に従い、プリント配線板にも、それに適応した性能が求められている。プリント配線板を形成する絶縁材料として熱硬化性樹脂組成物の硬化物が用いられ、熱硬化性樹脂組成物の中でも、価格面や接着性などの観点からエポキシ系化合物を含有するエポキシ系樹脂組成物が汎用されている。とりわけ近年は電子機器の薄型化、小型化、高性能化に合わせて配線板の多層化が進んでいる。 In accordance with recent improvements in performance of information communication equipment such as higher functionality and higher density, printed wiring boards are also required to have performance adapted to them. A cured product of a thermosetting resin composition is used as an insulating material for forming a printed wiring board. Among thermosetting resin compositions, an epoxy resin composition containing an epoxy compound from the viewpoint of price and adhesiveness. Goods are widely used. In particular, in recent years, multilayered wiring boards have been developed in accordance with the reduction in thickness, size, and performance of electronic devices.
こうしたエポキシ系樹脂組成物における硬化剤として、例えば、特許文献1には、活性エステル樹脂を用いることが記載されている。特許文献1に開示されるエステル樹脂を用いることによって、その硬化物において低誘電率、低誘電正接でありながら、優れた耐熱性と難燃性とを兼備させた熱硬化性樹脂組成物が得られるとされている。 As a curing agent in such an epoxy resin composition, for example, Patent Document 1 describes using an active ester resin. By using the ester resin disclosed in Patent Document 1, a thermosetting resin composition having both excellent heat resistance and flame retardancy while having a low dielectric constant and low dielectric loss tangent in the cured product is obtained. It is supposed to be done.
特許文献1には、上記のエステル樹脂は、フェノール性水酸基を含有する物質と、芳香族ジカルボン酸または芳香族ジカルボン酸塩化物とを反応させることによって生成することが記載されている。 Patent Document 1 describes that the ester resin is produced by reacting a substance containing a phenolic hydroxyl group with an aromatic dicarboxylic acid or an aromatic dicarboxylic acid chloride.
一方、特許文献2には、高温高湿環境下での吸湿後も優れた誘電特性(低誘電率・低誘電正接)を有し、かつ高いガラス転移温度と難燃性を有する硬化物を与える芳香族ビニルベンジルエーテル化合物が記載されている。 On the other hand, Patent Document 2 gives a cured product having excellent dielectric properties (low dielectric constant and low dielectric loss tangent) even after moisture absorption in a high temperature and high humidity environment, and having a high glass transition temperature and flame retardancy. Aromatic vinyl benzyl ether compounds are described.
本発明は、優れた誘電特性および優れた耐熱性を備える硬化物を形成可能な熱硬化性樹脂組成物の成分として有用な活性エステル樹脂、その活性エステル樹脂の製造方法、その活性エステル樹脂を製造するための原料の1種であるビニルベンジル化フェノール化合物、そのビニルベンジル化フェノール化合物の製造方法、上記の活性エステル樹脂を含有する熱硬化性樹脂組成物、当該熱硬化性樹脂組成物の硬化物、当該熱硬化性樹脂組成物を用いてなる層間絶縁材料、当該熱硬化性樹脂組成物を用いてなるプリプレグ、および当該プリプレグの製造方法を提供することを課題とする。 The present invention relates to an active ester resin useful as a component of a thermosetting resin composition capable of forming a cured product having excellent dielectric properties and excellent heat resistance, a method for producing the active ester resin, and producing the active ester resin. A vinylbenzylated phenol compound, a method for producing the vinylbenzylated phenol compound, a thermosetting resin composition containing the above active ester resin, and a cured product of the thermosetting resin composition It is an object of the present invention to provide an interlayer insulation material using the thermosetting resin composition, a prepreg using the thermosetting resin composition, and a method for producing the prepreg.
上記の課題を解決するために提供される本発明は次のとおりである。
[1]下記一般式(1)で示されるビニルベンジル化フェノール化合物。
[1] A vinylbenzylated phenol compound represented by the following general formula (1).
[2]上記[1]に記載されるビニルベンジル化フェノール化合物の製造方法であって、単環または多環の芳香核を2個以上有する2官能フェノール化合物およびビニルベンジルハライド化合物を、ハイドロタルサイト類を脱ハロゲン化水素剤として反応させること
を特徴とするビニルベンジル化フェノール化合物の製造方法。
[2] A method for producing a vinylbenzylated phenol compound as described in [1] above, wherein a bifunctional phenol compound having two or more monocyclic or polycyclic aromatic nuclei and a vinylbenzyl halide compound are hydrotalcite. A method for producing a vinylbenzylated phenol compound, which comprises reacting a compound as a dehydrohalogenating agent.
[3]前記単環または多環の芳香核を2個以上有する2官能フェノール化合物は、下記一般式(5)または下記一般式(12)で示される、上記[2]に記載のビニルベンジル化フェノール化合物の製造方法。
[4]下記一般式(6)で示される成分を含有することを特徴とする活性エステル樹脂。
[5]前記一般式(6)中のXは前記一般式(13)で示される構造である、上記[4]に記載の活性エステル樹脂。 [5] The active ester resin according to the above [4], wherein X in the general formula (6) is a structure represented by the general formula (13).
[6]上記[1]に記載されるビニルベンジル化フェノール化合物と、1官能フェノール化合物と、芳香核含有ジカルボン酸およびそのハライド化合物からなる群から選ばれる1種以上と、を反応させることを特徴とする、活性エステル樹脂の製造方法。 [6] The vinylbenzylated phenol compound described in [1] above, a monofunctional phenol compound, and one or more selected from the group consisting of an aromatic nucleus-containing dicarboxylic acid and a halide compound thereof are reacted. And a method for producing an active ester resin.
[7]上記[4]または上記[5]に記載される活性エステル樹脂とエポキシ樹脂とを含むことを特徴とする熱硬化性樹脂組成物。 [7] A thermosetting resin composition comprising the active ester resin described in [4] or [5] and an epoxy resin.
[8]さらに硬化促進剤を含む、上記[7]に記載の熱硬化性樹脂組成物。 [8] The thermosetting resin composition according to [7], further including a curing accelerator.
[9]さらに無機充填材を含む、上記[7]または上記[8]に記載の熱硬化性樹脂組成物。 [9] The thermosetting resin composition according to [7] or [8], further including an inorganic filler.
[10]上記[7]から上記[9]のいずれかに記載される熱硬化性樹脂組成物の硬化物。 [10] A cured product of the thermosetting resin composition according to any one of [7] to [9].
[11]上記[7]から上記[9]のいずれかに記載される熱硬化性樹脂組成物を含有することを特徴とする層間絶縁材料。 [11] An interlayer insulating material comprising the thermosetting resin composition according to any one of [7] to [9].
[12]上記[7]から上記[9]のいずれかに記載される熱硬化性樹脂組成物の半硬化体と繊維状補強部材とを備えることを特徴とするプリプレグ。 [12] A prepreg comprising a semi-cured body of the thermosetting resin composition described in any one of [7] to [9] above and a fibrous reinforcing member.
[13]上記[7]から上記[9]のいずれかに記載される熱硬化性樹脂組成物を繊維状補強材に含浸させ加熱して、前記繊維状補強材に含浸した前記熱硬化性樹脂組成物を半硬化することを特徴とするプリプレグの製造方法。 [13] The thermosetting resin impregnated in the fibrous reinforcing material by impregnating the thermosetting resin composition described in any of [7] to [9] above into a fibrous reinforcing material and heating. A method for producing a prepreg, comprising semi-curing the composition.
[14]上記[1]の一般式(1)のカッコ内に示される構造部位の芳香核への結合数が異なる複数種類の化合物を含む組成物であって、前記構造部位の平均繰り返し数が0.1〜4である組成物。 [14] A composition comprising a plurality of types of compounds having different numbers of bonds to the aromatic nucleus of the structural site shown in parentheses in the general formula (1) of [1] above, wherein the average number of repetitions of the structural site is The composition which is 0.1-4.
本発明によれば、優れた誘電特性(誘電率、誘電正接)および優れた耐熱性(ガラス転移温度、高温環境下での重量減少)を備える硬化物を形成可能な熱硬化性樹脂組成物の成分として有用な活性エステル樹脂、その活性エステル樹脂の製造方法、その活性エステル樹脂を製造するための原料の1種であるビニルベンジル化フェノール化合物、そのビニルベンジル化フェノール化合物の製造方法、上記の活性エステル樹脂を含有する熱硬化性樹脂組成物、当該熱硬化性樹脂組成物の硬化物、当該熱硬化性樹脂組成物を用いてなる層間絶縁材料、当該熱硬化性樹脂組成物を用いてなるプリプレグ、および当該プリプレグの製造方法が提供される。 According to the present invention, there is provided a thermosetting resin composition capable of forming a cured product having excellent dielectric properties (dielectric constant, dielectric loss tangent) and excellent heat resistance (glass transition temperature, weight loss under high temperature environment). Active ester resin useful as a component, method for producing the active ester resin, vinylbenzylated phenol compound as one of raw materials for producing the active ester resin, method for producing the vinylbenzylated phenol compound, the above-mentioned activity A thermosetting resin composition containing an ester resin, a cured product of the thermosetting resin composition, an interlayer insulating material using the thermosetting resin composition, and a prepreg using the thermosetting resin composition And a method for producing the prepreg.
以下、本発明の実施形態を説明する。 Embodiments of the present invention will be described below.
本発明の一実施形態に係るビニルベンジル化フェノール化合物(a)は、下記一般式(1)で示される。
上記一般式(1)中、Ar0は単環または多環の芳香核を2個以上有する2官能フェノール化合物残基であって、下記一般式(3)または下記一般式(11)で示される構造を有する。R1〜R5は同一または異なってもよく、水素またはメチル基である。pは1〜4の整数である。本発明の一実施形態に係る組成物は、上記一般式(1)のカッコ内に示される構造部位の芳香核への結合数が異なる複数種類の化合物を含み、前記構造部位の平均繰り返し数が0.1〜4である。なお、平均繰り返し数が非整数となるのは、ビニルベンジル化フェノール化合物(a)は、上記一般式(1)のカッコ内に示される構造部位の芳香核への結合数が異なる複数種類の化合物を含む組成物からなる場合があるためである。他の一般式における平均繰り返し数についても同様である。
上記一般式(3)における2つの水酸基の芳香核上の位置は任意である。上記一般式(3)中のYは、下記一般式(22)または下記化学式(23)で表される構造である。
上記一般式(22)におけるR30〜R33は、同一または異なってもよく、水素またはメチル基である。
上記一般式(11)中のZは、直接結合、−(CH2)−、−C(CH3)2−、−CH(CH3)−、−CH(Ph)−、−C(CH3)(Ph)−、フルオレニル基、シクロヘキシリデン基、もしくは3,3,5−トリメチルシクロへキシリデン基、または下記一般式(21)、上記一般式(22)もしくは上記化学式(23)で表される構造である。
上記一般式(21)におけるR26〜R29は、同一または異なってもよく、水素またはメチル基である。上記一般式(21)の具体例として、1,3−フェニレンジイソプロピリデン基、1,4−フェニレンジイソプロピリデン基などが挙げられる。 R 26 to R 29 in the general formula (21) may be the same or different and are hydrogen or a methyl group. Specific examples of the general formula (21) include a 1,3-phenylene diisopropylidene group and a 1,4-phenylene diisopropylidene group.
上記の本発明の一実施形態に係るビニルベンジル化フェノール化合物(a)の製造方法は限定されない。次に説明する製造方法により、ビニルベンジル化フェノール化合物(a)を効率的に製造することができる。 The method for producing the vinylbenzylated phenol compound (a) according to one embodiment of the present invention is not limited. The vinylbenzylated phenol compound (a) can be efficiently produced by the production method described below.
ビニルベンジル化フェノール化合物(a)の本発明の一実施形態に係る製造方法では、下記一般式(5)または下記一般式(12)で示される単環または多環の芳香核を2個以上有する2官能フェノール化合物(α)およびビニルベンジルハライド化合物(β)を、ハイドロタルサイト類(γ)を脱ハロゲン化水素剤として反応させる。
ここで、上記一般式(5)中のYは、下記一般式(22)または下記化学式(23)で表される構造を含む。
上記一般式(22)におけるR30〜R33は、同一または異なってもよく、水素またはメチル基である。
上記一般式(12)中のZは、直接結合、−(CH2)−、−C(CH3)2−、−CH(CH3)−、−CH(Ph)−、−C(CH3)(Ph)−、フルオレニル基、シクロヘキシリデン基、もしくは3,3,5−トリメチルシクロへキシリデン基、または下記一般式(21)、上記一般式(22)もしくは上記化学式(23)で表される構造である。
上記一般式(21)におけるR26〜R29は、同一または異なってもよく、水素またはメチル基である。 R 26 to R 29 in the general formula (21) may be the same or different and are hydrogen or a methyl group.
ビニルベンジルハライド化合物(β)は、芳香核にビニル基およびハロゲン化メチル基が結合していればよく、ビニル基とハロゲン化メチル基との位置関係は限定されない。 The vinyl benzyl halide compound (β) is not limited as long as the vinyl group and the halogenated methyl group are bonded to the aromatic nucleus, and the positional relationship between the vinyl group and the halogenated methyl group is not limited.
本発明の一実施形態に係る製造方法では、上記の2官能フェノール化合物(α)とビニルベンジルハライド化合物(β)との反応における脱ハロゲン化水素剤として、ハイドロタルサイト類(γ)を用いる。ハイドロタルサイト類(γ)はマグネシウムおよびアルミニウムの炭酸塩および水酸化物の複合体の水和物であり、その一般式としてはMg6Al12(OH)16(CO3)・4H2O、Mg4.5Al2(OH)13CO3・qH2O(qは3〜3.5)である。また、それらの無水化物の例としては、Mg0.7Al0.3O1.15が挙げられる。ハイドロタルサイト類(γ)の具体例となる製品としては、KW−500SH、KW−500SN、KW−500PL、KW−500G−7、KW−1000、KW−1015、KW−2000、KW−2100(いずれも協和化学工業社製)が挙げられる。ハイドロタルト類(γ)を脱ハロゲン化水素剤として用いることにより、2官能フェノール化合物(α)のフェノール性水酸基を残したまま、ビニルベンジルハライド化合物(β)に基づく残基を芳香核の骨格に直接的に結合させることが実現される。 In the production method according to an embodiment of the present invention, hydrotalcites (γ) are used as a dehydrohalogenating agent in the reaction of the bifunctional phenol compound (α) and the vinylbenzyl halide compound (β). Hydrotalcite (γ) is a hydrate of a complex of magnesium and aluminum carbonate and hydroxide, and the general formula thereof is Mg 6 Al 12 (OH) 16 (CO 3 ) · 4H 2 O, mg 4.5 Al 2 (OH) 13 CO 3 · qH 2 O (q is 3 to 3.5) is. Moreover, Mg 0.7 Al 0.3 O 1.15 is mentioned as an example of those anhydrides. Specific examples of hydrotalcites (γ) include KW-500SH, KW-500SN, KW-500PL, KW-500G-7, KW-1000, KW-1015, KW-2000, KW-2100 ( Both are manufactured by Kyowa Chemical Industry Co., Ltd.). By using hydrotalts (γ) as a dehydrohalogenating agent, residues based on the vinylbenzyl halide compound (β) can be used as the skeleton of the aromatic nucleus while leaving the phenolic hydroxyl group of the bifunctional phenol compound (α). Direct coupling is realized.
この点に関し、例えば特許文献2に記載される芳香族ビニルベンジルエーテル化合物は多価フェノール化合物とビニルベンジルハライドとから形成され、水酸化ナトリウムなどのアルカリ金属水酸化物を脱ハロゲン化水素剤として用いることにより、多価フェノール化合物におけるフェノール性水酸基とビニルベンジルハライドのハロゲンとが反応して、エーテル結合が形成される。このような反応では、多価フェノール化合物の一部を消費する形でビニル基を導入することになり、その後の活性エステル樹脂の構造制御性が低くなってしまう。これに対し、本発明の一実施形態に係る製造方法によれば、活性エステル樹脂を形成するための反応の際に、2官能フェノール化合物(α)が有するフェノール性水酸基をカルボン酸ハロゲン化物との反応点とすることができるため、活性エステル樹脂の分子設計が容易となる。 In this regard, for example, the aromatic vinyl benzyl ether compound described in Patent Document 2 is formed from a polyhydric phenol compound and vinyl benzyl halide, and an alkali metal hydroxide such as sodium hydroxide is used as a dehydrohalogenating agent. As a result, the phenolic hydroxyl group in the polyhydric phenol compound reacts with the halogen of vinylbenzyl halide to form an ether bond. In such a reaction, a vinyl group is introduced in a form that consumes a part of the polyhydric phenol compound, and the structure controllability of the active ester resin thereafter is lowered. On the other hand, according to the production method according to one embodiment of the present invention, the phenolic hydroxyl group of the bifunctional phenol compound (α) is converted to the carboxylic acid halide during the reaction for forming the active ester resin. Since it can be a reaction point, the molecular design of the active ester resin is facilitated.
2官能フェノール化合物(α)とビニルベンジルハライド化合物(β)との反応における原料の仕込み量や反応条件は、所望の反応生成物の構造に応じて、ハイドロタルサイト類(γ)による脱ハロゲン化水素反応が適切に進行するように適宜設定される。2官能フェノール化合物(α)の仕込み量に対するビニルベンジルハライド化合物(β)の仕込み量のモル比率(β/α)は、0.1〜2.0とすることが好ましい場合がある。ハイドロタルサイト類(γ)の使用量のビニルベンジルハライド化合物(β)の仕込み量に対するモル比率(γ/β)は、0.70〜1.50とすることが好ましい場合がある。ハイドロタルサイト類(γ)を脱ハロゲン化水素剤として用いる場合には、脱ハロゲン化水素反応が二酸化炭素および水の発生を伴うため、反応中における炭酸ガスの発生を適切に制御することや、水分を適切に系外に排出することなどを考慮して、加熱温度などの反応条件を設定することが好ましい。 Depending on the structure of the desired reaction product, the raw material charge amount and reaction conditions in the reaction between the bifunctional phenol compound (α) and the vinylbenzyl halide compound (β) are dehalogenated with hydrotalcites (γ). It is suitably set so that the hydrogen reaction proceeds appropriately. The molar ratio (β / α) of the charged amount of the vinylbenzyl halide compound (β) to the charged amount of the bifunctional phenol compound (α) may be preferably 0.1 to 2.0. The molar ratio (γ / β) of the usage amount of the hydrotalcite (γ) to the charged amount of the vinylbenzyl halide compound (β) may preferably be 0.70 to 1.50. When hydrotalcite (γ) is used as a dehydrohalogenating agent, the dehydrohalogenation reaction involves the generation of carbon dioxide and water, so the generation of carbon dioxide gas during the reaction is appropriately controlled, It is preferable to set reaction conditions such as heating temperature in consideration of appropriately discharging moisture out of the system.
限定されない例示を行えば、脱ハロゲン化水素反応は、2官能フェノール化合物(α)およびハイドロタルサイト類(γ)を含有するスラリー状の反応液を50℃〜80℃の範囲内、好ましくは60℃〜70℃の範囲内に維持しつつ、ビニルベンジルハライド化合物(β)を滴下することにより、急激な炭酸ガスの発生を抑制することができる。また、上記のスラリー状の反応液における溶媒をトルエンやメチルイソブチルケトンなどとし、ビニルベンジルハライド化合物(β)を全量滴下した後、反応液の温度を100℃以上に加温して、反応液内の水分を除去することが好ましい。 As a non-limiting example, the dehydrohalogenation reaction is carried out using a slurry-like reaction solution containing a bifunctional phenol compound (α) and hydrotalcites (γ) within a range of 50 ° C. to 80 ° C., preferably 60 While maintaining the temperature within a range of from ℃ to 70 ℃, drastic generation of carbon dioxide can be suppressed by dropping the vinylbenzyl halide compound (β). Further, the solvent in the slurry-like reaction solution is toluene or methyl isobutyl ketone, and after all the vinylbenzyl halide compound (β) is dropped, the temperature of the reaction solution is heated to 100 ° C. or higher, and the reaction solution is heated. It is preferable to remove the moisture.
2官能フェノール化合物(α)とビニルベンジルハライド化合物(β)との反応に用いる溶媒としては、トルエン、キシレン、メシチレン、エチルベンゼン、メチルイソブチルケトン、メチルn‐アミルケトン、メチルイソアミルケトンなどが挙げられる。 Examples of the solvent used for the reaction between the bifunctional phenol compound (α) and the vinylbenzyl halide compound (β) include toluene, xylene, mesitylene, ethylbenzene, methyl isobutyl ketone, methyl n-amyl ketone, and methyl isoamyl ketone.
本発明の一実施形態に係る活性エステル樹脂(A)は、下記一般式(6)で示される構造を有する成分を含有する。
上記一般式(6)中、Xは下記一般式(8)または下記一般式(13)で示される構造である。Ar1およびAr2は同一または異なってもよく、フェニル基、芳香核上に炭素原子数1〜4のアルキル基を1〜3個有するフェニル基、ナフチル基、または芳香核上に炭素原子数1〜4のアルキル基を1〜3個有するナフチル基である。平均繰り返し数nは0.5〜30である。
上記一般式(8)中、R6〜R15は同一または異なってもよく、水素またはメチル基である。平均繰り返し数lおよび平均繰り返し数kはそれぞれ独立に0.1〜2である。上記一般式(8)中のYは、上記一般式(3)や上記一般式(5)におけるYと同様であって、下記一般式(22)または下記化学式(23)で表される構造である。
上記一般式(22)および上記化学式(23)におけるR30〜R33は、同一または異なってもよく、水素またはメチル基である。
上記一般式(13)中、Zは、直接結合、−(CH2)−、−C(CH3)2−、−CH(CH3)−、−CH(Ph)−、−C(CH3)(Ph)−、フルオレニル基、シクロヘキシリデン基、もしくは3,3,5−トリメチルシクロへキシリデン基、または下記一般式(21)、上記一般式(22)もしくは上記化学式(23)で表される構造であり、R16〜R25は、同一または異なってもよく、水素またはメチル基であり、平均繰り返し数j、iはそれぞれ独立に0.1〜2である。
上記一般式(21)におけるR26〜R29は、同一または異なってもよく、水素またはメチル基である。 R 26 to R 29 in the general formula (21) may be the same or different and are hydrogen or a methyl group.
本発明の一実施形態に係る活性エステル樹脂(A)は、特許文献1に開示される活性エステル樹脂と異なり、重合反応が可能なビニル基をベンジル基の芳香核に有している。このため、ビニル基の二重結合を反応部位とする反応が進行した場合に、その反応により形成された炭素鎖と、活性エステル樹脂(A)のエステル結合を含む主鎖との相対位置が変化しにくい。それゆえ、本発明の一実施形態に係る活性エステル樹脂(A)を含む熱硬化性樹脂組成物の硬化物は、加熱された際に、変形や分解が生じにくく、ガラス転移温度が高く耐熱安定性に優れる材料となりやすい。活性エステル樹脂(A)の主鎖の動きにくさ(主鎖を回転軸とする回転のしにくさなど)をより安定的に高める観点から、本発明の一実施形態に係る活性エステル樹脂(A)は、上記一般式(6)中のXが上記一般式(7)で示される構造であることが好ましい場合もある。 Unlike the active ester resin disclosed in Patent Document 1, the active ester resin (A) according to an embodiment of the present invention has a vinyl group capable of polymerization reaction in the aromatic nucleus of the benzyl group. For this reason, when the reaction using the double bond of the vinyl group proceeds, the relative position between the carbon chain formed by the reaction and the main chain containing the ester bond of the active ester resin (A) changes. Hard to do. Therefore, the cured product of the thermosetting resin composition containing the active ester resin (A) according to an embodiment of the present invention is not easily deformed or decomposed when heated, has a high glass transition temperature, and is heat resistant and stable. It is easy to become a material with excellent properties. From the viewpoint of more stably increasing the difficulty of movement of the main chain of the active ester resin (A) (such as the difficulty of rotation using the main chain as the rotation axis), the active ester resin (A ) May preferably have a structure in which X in the general formula (6) is represented by the general formula (7).
本発明の一実施形態に係る活性エステル樹脂(A)の製造方法は限定されない。例えば、本発明の一実施形態に係るビニルベンジル化フェノール化合物(a)と、1官能フェノール化合物(b)と、芳香核含有ジカルボン酸およびそのハライド化合物からなる群から選ばれる1種からなる芳香族カルボン酸系化合物(c)以上とを反応させることによって、活性エステル樹脂(A)を得ることができる。 The manufacturing method of active ester resin (A) which concerns on one Embodiment of this invention is not limited. For example, an aromatic composed of one kind selected from the group consisting of a vinylbenzylated phenol compound (a), a monofunctional phenol compound (b), an aromatic nucleus-containing dicarboxylic acid and a halide compound thereof according to an embodiment of the present invention. The active ester resin (A) can be obtained by reacting the carboxylic acid compound (c) or higher.
1官能フェノール化合物(b)の具体例として、フェノール、ナフトール等の無置換1官能フェノール化合物、およびクレゾール、ジメチルフェノール、エチルフェノール等のアルキル置換1官能フェノール化合物が挙げられる。アルキル置換1官能フェノール化合物におけるアルキル基の置換数は3以下であってアルキル基の炭素数は4以下であることが、後述するエポキシ樹脂(B)との硬化性および誘電特性のバランスの観点から好ましい場合がある。 Specific examples of the monofunctional phenol compound (b) include unsubstituted monofunctional phenol compounds such as phenol and naphthol, and alkyl-substituted monofunctional phenol compounds such as cresol, dimethylphenol, and ethylphenol. In the alkyl-substituted monofunctional phenolic compound, the number of substitution of the alkyl group is 3 or less, and the number of carbon atoms of the alkyl group is 4 or less, from the viewpoint of balance between curability and dielectric properties with the epoxy resin (B) described later. It may be preferable.
芳香族カルボン酸系化合物(c)の具体例として、フタル酸、イソフタル酸、テレフタル酸、2,6−ナフタレンジカルボン酸、1,6−ナフタレンジカルボン酸、2,7−ナフタレンジカルボン酸、ジフェニルエーテル4,4’−ジカルボン酸、4,4’−ビフェニルジカルボン酸、およびこれらの酸塩化物が挙げられる。 Specific examples of the aromatic carboxylic acid compound (c) include phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl ether 4, Examples include 4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and acid chlorides thereof.
上記反応の条件は、活性エステル樹脂(A)を適切に生成できる限り、任意である。多官能フェノール化合物(特許文献1におけるフェノール性水酸基含有樹脂が例示される。)と1官能フェノール化合物(b)と芳香族カルボン酸系化合物(c)とを反応させることにより活性エステル樹脂が得られることは公知であるから、その製造方法を参考にしてもよい。 The reaction conditions are arbitrary as long as the active ester resin (A) can be appropriately generated. An active ester resin is obtained by reacting a polyfunctional phenol compound (the phenolic hydroxyl group-containing resin in Patent Document 1 is exemplified), a monofunctional phenol compound (b), and an aromatic carboxylic acid compound (c). Since this is well-known, you may refer to the manufacturing method.
本発明の一実施形態に係る熱硬化性樹脂組成物は、本発明の一実施形態に係る活性エステル樹脂(A)およびエポキシ樹脂(B)を含有する。 The thermosetting resin composition according to an embodiment of the present invention contains an active ester resin (A) and an epoxy resin (B) according to an embodiment of the present invention.
エポキシ樹脂(B)は公知のものを使用することができる。例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、フェノールビフェニルアラルキル型エポキシ樹脂、フェノール、ナフトールなどのキシリレン結合によるアラルキル樹脂のエポキシ化物、ジシクロペンタジエン変性フェノール樹脂のエポキシ化物、ジヒドロキシナフタレン型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂などのグリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂などの2価以上のエポキシ基を有するエポキシ樹脂が挙げることができる。これらエポキシ樹脂は単独でも2種類以上を併用してもよい。 A well-known thing can be used for an epoxy resin (B). For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, aralkyl resin epoxy with xylylene bonds such as phenol and naphthol Epoxides of dicyclopentadiene-modified phenolic resins, dihydroxynaphthalene type epoxy resins, glycidyl ether type epoxy resins such as triphenolmethane type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins and other bivalent or more epoxies An epoxy resin having a group can be mentioned. These epoxy resins may be used alone or in combination of two or more.
これらエポキシ樹脂(B)の中でも、フェノールビフェニルアラルキル型エポキシ樹脂、フェノール、ナフトールなどのキシリレン結合によるアラルキル樹脂のエポキシ化物、ジシクロペンタジエン変性フェノール樹脂のエポキシ化物のようなエポキシ当量が大きい樹脂を使用するのが好ましい。良好な誘電特性を得る観点からである。 Among these epoxy resins (B), resins having a large epoxy equivalent, such as phenol biphenyl aralkyl type epoxy resins, epoxidized aralkyl resins by xylylene bonds such as phenol and naphthol, and epoxidized products of dicyclopentadiene-modified phenol resins are used. Is preferred. This is from the viewpoint of obtaining good dielectric properties.
本発明の一実施形態に係る熱硬化性樹脂組成物における、活性エステル樹脂(A)とエポキシ樹脂(B)の配合比は、活性エステル樹脂(A)に含まれるエステル基とエポキシ樹脂(B)に含まれるエポキシ基の当量比(B/A)が0.5〜1.5の範囲にあることが好ましく、0.8〜1.2の範囲にあることが特に好ましい。 In the thermosetting resin composition according to one embodiment of the present invention, the compounding ratio of the active ester resin (A) and the epoxy resin (B) is the ester group contained in the active ester resin (A) and the epoxy resin (B). The equivalent ratio (B / A) of the epoxy groups contained in is preferably in the range of 0.5 to 1.5, particularly preferably in the range of 0.8 to 1.2.
本発明の一実施形態に係る熱硬化性樹脂組成物は、さらに硬化促進剤を含んでいてもよい。かかる硬化促進剤の例としては、活性エステル樹脂(A)に含まれるビニル基の反応を促進する観点から、ハイドロパーオキサイド、ジアルキルパーオキサイド等有機過酸化物、アゾ化合物、トリアルキルボラン等有機ホウ素化合物などが挙げられる。また、活性エステル樹脂(A)に含まれるエステル基とエポキシ樹脂(B)の硬化促進剤として公知の物質を用いることができる。この様な硬化促進剤としては例えば、3級アミン化合物、4級アンモニウム塩、イミダゾール類、ホスフィン化合物、ホスホニウム塩などを挙げることができる。より具体的には、トリエチルアミン、トリエチレンジアミン、ベンジルジメチルアミン、4−ジメチルアミノピリジン、2,4,6−トリス(ジメチルアミノメチル)フェノール、1,8−ジアザビシクロ(5,4,0)ウンデセン−7などの3級アミン化合物、2−メチルイミダゾール、2,4−ジメチルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾールなどのイミダゾール類、トリフェニルホスフィン、トリブチルホスフィン、トリ(p−メチルフェニル)ホスフィン、トリ(ノニルフェニル)ホスフィンなどのホスフィン化合物、テトラフェニルホスホニウムテトラフェニルボレ−ト、テトラフェニルホスホニウムテトラナフトエ酸ボレ−トなどのホスホニウム塩、トリフェニルホスホニオフェノラ−ト、ベンゾキノンとトリフェニルホスフィンの反応物などのベタイン状有機リン化合物を挙げることができる。 The thermosetting resin composition according to one embodiment of the present invention may further contain a curing accelerator. Examples of such curing accelerators include organic peroxides such as hydroperoxides and dialkyl peroxides, azo compounds, and organic borons such as trialkylboranes from the viewpoint of promoting the reaction of vinyl groups contained in the active ester resin (A). Compound etc. are mentioned. Moreover, a well-known substance can be used as a hardening accelerator of the ester group and epoxy resin (B) which are contained in active ester resin (A). Examples of such curing accelerators include tertiary amine compounds, quaternary ammonium salts, imidazoles, phosphine compounds, and phosphonium salts. More specifically, triethylamine, triethylenediamine, benzyldimethylamine, 4-dimethylaminopyridine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 Tertiary amine compounds such as 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, triphenylphosphine, Phosphonium compounds such as tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphoniumtetranaphthoic acid borate, etc. It can be mentioned bets, betaine-like organic phosphorus compounds such as the reaction product of benzoquinone and triphenyl phosphine - salt, triphenylphosphonio phenolate la.
上記の硬化促進剤の使用量は限定されない。硬化促進剤の機能に応じて適宜設定されるべきものである。 The usage-amount of said hardening accelerator is not limited. It should be appropriately set according to the function of the curing accelerator.
本発明の一実施形態に係る熱硬化性樹脂組成物は、さらに無機充填剤を含んでいてもよい。かかる無機充填剤としては、非晶性シリカ、結晶性シリカ、アルミナ、ガラス、珪酸カルシウム、石膏、炭酸カルシウム、マグネサイト、クレー、タルク、マイカ、マグネシア、または硫酸バリウムなどを挙げることができる。中でも、非晶性シリカ、結晶性シリカなどが好ましい。 The thermosetting resin composition according to one embodiment of the present invention may further contain an inorganic filler. Examples of the inorganic filler include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, talc, mica, magnesia, or barium sulfate. Among these, amorphous silica and crystalline silica are preferable.
また優れた成形性を維持しつつ、充填剤の配合量を高めるためには、細密充填を可能とするような粒度分布の広い球形の充填剤を使用することが好ましい。その場合、粒径が0.1〜3μmの小粒径の球形無機充填剤5〜40重量%、粒径が5〜30μmの大粒径の球形無機充填剤95〜60重量%の割合で混合して使用するのが好ましい。 In order to increase the blending amount of the filler while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution that enables fine packing. In that case, a small inorganic particle size spherical filler having a particle size of 0.1 to 3 μm is mixed in a proportion of 5 to 40% by weight, and a large particle size spherical inorganic filler having a particle size of 5 to 30 μm is mixed in a proportion of 95 to 60% by weight. And preferably used.
本発明の一実施形態に係る熱硬化性樹脂組成物が無機充填剤を含有する場合において、無機充填剤の配合量は無機充填剤の種類や用途などに応じて適宜設定される。限定されない例として、無機充填剤の配合量を熱硬化性樹脂組成物全体の60質量%〜93質量%とすることが挙げられる。 In the case where the thermosetting resin composition according to one embodiment of the present invention contains an inorganic filler, the blending amount of the inorganic filler is appropriately set according to the type and application of the inorganic filler. As an example which is not limited, it is mentioned that the compounding quantity of an inorganic filler shall be 60 mass%-93 mass% of the whole thermosetting resin composition.
本発明の一実施形態に係る熱硬化性樹脂組成物には、さらに必要に応じて、溶剤、カップリング剤、離型剤、着色剤、難燃剤、低応力剤、増粘剤などを添加、あるいは予め反応して用いることができる。カップリング剤の例としては、ビニルシラン系、アミノシラン系、エポキシシラン系等のシラン系カップリング剤、チタン系カップリングなどが挙げられる。離型剤の例としてはカルナバワックス、パラフィンワックス、ステアリン酸、モンタン酸、カルボキシル基含有ポリオレフィンワックスなどが挙げられる。また着色剤としては、カーボンブラックなどが挙げられる。難燃剤の例としては、ハロゲン化エポキシ樹脂、ハロゲン化合物、リン化合物など、また難燃助剤としては三酸化アンチモンなどが挙げられる。低応力剤の例としては、シリコンゴム、変性ニトリルゴム、変性ブタジエンゴム、変性シリコンオイルなどが挙げられる。 To the thermosetting resin composition according to an embodiment of the present invention, a solvent, a coupling agent, a release agent, a colorant, a flame retardant, a low stress agent, a thickener, and the like are further added as necessary. Or it can react and use beforehand. Examples of the coupling agent include silane coupling agents such as vinyl silane, amino silane, and epoxy silane, titanium coupling, and the like. Examples of the mold release agent include carnauba wax, paraffin wax, stearic acid, montanic acid, carboxyl group-containing polyolefin wax, and the like. Examples of the colorant include carbon black. Examples of the flame retardant include halogenated epoxy resins, halogen compounds, and phosphorus compounds, and examples of the flame retardant aid include antimony trioxide. Examples of the low stress agent include silicon rubber, modified nitrile rubber, modified butadiene rubber, and modified silicone oil.
本発明の一実施形態に係る熱硬化性樹脂組成物を加熱することにより、硬化物を得ることができる。かかる本発明の一実施形態に係る硬化物は、ビニル基を有する活性エステル樹脂(A)に由来する構造部分を有するため、誘電率が低い、誘電正接が低い、など誘電特性に優れる。 A cured product can be obtained by heating the thermosetting resin composition according to one embodiment of the present invention. Such a cured product according to one embodiment of the present invention has a structural portion derived from the active ester resin (A) having a vinyl group, and therefore has excellent dielectric properties such as low dielectric constant and low dielectric loss tangent.
また、活性エステル樹脂(A)はビニルベンジル基が芳香核に直接結合した構造を有するため、ビニル基が重合反応した際に形成される炭素鎖が、水酸基を利用して導入したビニルベンジルエーテルと比較して分子運動しにくい。このため、本発明の一実施形態に係る硬化物が加熱されても、硬化物における活性エステル樹脂(A)に由来する構造部分は回転運動などが生じにくい。それゆえ、本発明の一実施形態に係る硬化物は、ガラス転移温度が高くなりやすく、耐熱安定性にも優れたものとなりやすい。 In addition, since the active ester resin (A) has a structure in which a vinylbenzyl group is directly bonded to an aromatic nucleus, a carbon chain formed when the vinyl group undergoes a polymerization reaction is a vinyl benzyl ether introduced using a hydroxyl group and Compared to molecular movement is difficult. For this reason, even if the hardened | cured material which concerns on one Embodiment of this invention is heated, the structure part derived from active ester resin (A) in hardened | cured material does not produce a rotational motion etc. easily. Therefore, the cured product according to an embodiment of the present invention tends to have a high glass transition temperature and excellent heat stability.
本発明の一実施形態に係る熱硬化性樹脂組成物を硬化させる温度は、その硬化物の組成に応じて適宜設定される。限定されない例示として、100〜250℃の温度範囲で加熱することが挙げられる。 The temperature at which the thermosetting resin composition according to one embodiment of the present invention is cured is appropriately set according to the composition of the cured product. A non-limiting example is heating in a temperature range of 100 to 250 ° C.
硬化のための具体的な作業も限定されない。例えば、本発明の一実施形態に係る熱硬化性樹脂組成物を必要に応じて溶媒で希釈し、得られた希釈溶液を基材に塗工して、加熱により乾燥、硬化させる。得られた硬化塗膜を基材から剥すことにより、本発明の一実施形態に係る硬化物(硬化物フィルム)を得ることができる。本発明の一実施形態に係る熱硬化性樹脂組成物を成形型内で硬化させることにより、成形材を得ることができる。本発明の一実施形態に係る熱硬化性樹脂組成物の硬化物をバインダーとしても用いてもよいし、コーティング材として用いてもよいし、硬化物を含む部材を積層材として用いてもよい。 The specific operation for curing is not limited. For example, the thermosetting resin composition according to one embodiment of the present invention is diluted with a solvent as necessary, the obtained diluted solution is applied to a substrate, and dried and cured by heating. By removing the obtained cured coating film from the substrate, a cured product (cured product film) according to one embodiment of the present invention can be obtained. A molding material can be obtained by curing the thermosetting resin composition according to an embodiment of the present invention in a mold. The cured product of the thermosetting resin composition according to one embodiment of the present invention may be used as a binder, may be used as a coating material, or a member including the cured product may be used as a laminated material.
本発明の一実施形態に係る層間絶縁材料は、本発明の一実施形態に係る熱硬化性樹脂組成物からなる。例えば、本発明の一実施形態に係る熱硬化性樹脂組成物を溶剤に溶解させることにより、回路基板に塗布して絶縁層とするための層間絶縁用ワニスとすることができる。 The interlayer insulation material which concerns on one Embodiment of this invention consists of a thermosetting resin composition which concerns on one Embodiment of this invention. For example, by dissolving the thermosetting resin composition according to one embodiment of the present invention in a solvent, an interlayer insulating varnish for applying to a circuit board to form an insulating layer can be obtained.
得られた層間絶縁用ワニスを支持フィルム上に展開したのち加熱処理してフィルム状とすれば、層間絶縁材料用途の接着シートとすることができる。この接着シートは多層プリント配線基板における層間絶縁材とすることができる。本発明の一実施形態に係る層間絶縁材料を、半導体封止用に使用する場合は、熱硬化性樹脂組成物は上述したような無機充填剤を含有することが好ましい。 If the obtained interlayer insulating varnish is spread on a support film and then heat-treated to form a film, an adhesive sheet for use as an interlayer insulating material can be obtained. This adhesive sheet can be used as an interlayer insulating material in a multilayer printed wiring board. When using the interlayer insulation material which concerns on one Embodiment of this invention for semiconductor sealing, it is preferable that a thermosetting resin composition contains an inorganic filler as mentioned above.
本発明の一実施形態に係るプリプレグは、本発明の一実施形態に係る熱硬化性樹脂組成物の半硬化体とガラス繊維など繊維状補強部材とを備える。このプリプレグは多層プリント配線基板における層間絶縁材とすることができる。本発明の一実施形態に係るプリプレグの製造方法は限定されない。本発明の一実施形態に係る熱硬化性樹脂組成物を、必要に応じて溶剤を加えてワニス状として、繊維状補強部材に含浸させて加熱処理を行うことにより、本発明の一実施形態に係るプリプレグを製造することができる。 A prepreg according to an embodiment of the present invention includes a semi-cured body of a thermosetting resin composition according to an embodiment of the present invention and a fibrous reinforcing member such as glass fiber. This prepreg can be used as an interlayer insulating material in a multilayer printed wiring board. The manufacturing method of the prepreg which concerns on one Embodiment of this invention is not limited. The thermosetting resin composition according to one embodiment of the present invention is made into a varnish by adding a solvent as necessary, and impregnated into a fibrous reinforcing member, and subjected to heat treatment, thereby achieving one embodiment of the present invention. Such a prepreg can be manufactured.
以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。 The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
以下、実施例等により本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.
<水酸基当量>
試料をピリジンと過剰の無水酢酸でアセチル化し、試料中に存在する水酸基に消費される無水酢酸から生成する酢酸を、水酸化カリウムアルコール溶液で滴定することで求めた。
<Hydroxyl equivalent>
The sample was acetylated with pyridine and excess acetic anhydride, and acetic acid produced from acetic anhydride consumed by hydroxyl groups present in the sample was determined by titration with a potassium hydroxide alcohol solution.
<GPC分析条件>
(1)使用機器:東ソー社製「HLC−8320 GPC」
(2)カラム:いずれも東ソー社製、「TSKgel superHZ4000」(1本)+「TSKgel superHZ3000」(1本)+「TSKgel superHZ2000」(2本)+「TSKgel superHZ1000」(1本)(各々6.0mm×15cmのカラムを接続)
(3)溶媒:テトラヒドロフラン
(4)流量:0.6ml/min
(5)温度:40℃
(6)検出器:示差屈折率(RI)計(測定装置「HLC−8320 GPC」内蔵RI検出器)
<GPC analysis conditions>
(1) Equipment used: “HLC-8320 GPC” manufactured by Tosoh Corporation
(2) Column: All manufactured by Tosoh Corporation, “TSKgel superHZ4000” (1) + “TSKgel superHZ3000” (1) + “TSKgel superHZ2000” (2) + “TSKgel superHZ1000” (1) (each 6) (Connect a column of 0mm x 15cm)
(3) Solvent: Tetrahydrofuran (4) Flow rate: 0.6 ml / min
(5) Temperature: 40 ° C
(6) Detector: differential refractive index (RI) meter (RI detector with built-in measuring device “HLC-8320 GPC”)
<FD‐MS分析条件>
(1)装置:日本電子製「JMS‐T100GCV」
(2)カソード電圧:−10kV
(3)エミッタ電流:0mA→35mA(51.2mA/min.)
(4)測定質量範囲:m/z=10〜2000(実施例1)
m/z=10〜3000(実施例5)
<FD-MS analysis conditions>
(1) Equipment: “JMS-T100GCV” manufactured by JEOL
(2) Cathode voltage: -10 kV
(3) Emitter current: 0 mA → 35 mA (51.2 mA / min.)
(4) Measurement mass range: m / z = 10 to 2000 (Example 1)
m / z = 10 to 3000 (Example 5)
(参考例1)
窒素ガス導入管、温度計および撹拌機を備えた四口の2Lフラスコに、2,7‐ジヒドロキシナフタレン160.2g、ハイドロタルサイト(協和化学工業社製「KW‐500SH)311.0g、およびトルエン1251.3gを仕込み、60〜70℃に昇温した。次いで、クロロメチルスチレン152.6g(AGCセイミケミカル社製「CMS‐P」)を炭酸ガスによる急激な発泡に注意しながら、滴下して添加した。さらに、100〜110℃の温度に昇温して、炭酸ガスおよび水を系外へ排出しながら5時間反応させた。得られた反応溶液からハイドロタルサイトを濾過して取り除いた後、トルエンでハイドロタルサイトを洗浄することで、2,7‐ジヒドロキシナフタレンのビニルベンジル化物溶液(A−1)1606.6gを得た。固形分収率78.5%、固形分13.5%、水酸基当量は、144.5g/eqであった。得られたビニルベンジル化物溶液(A−1)のGPCチャートを図1に示す。
(Reference Example 1)
In a four-necked 2 L flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 160.2 g of 2,7-dihydroxynaphthalene, 311.0 g of hydrotalcite (“KW-500SH” manufactured by Kyowa Chemical Industry Co., Ltd.), and toluene 1251.3 g was charged and the temperature was raised to 60 to 70 ° C. Next, 152.6 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was dropped while paying attention to rapid foaming by carbon dioxide gas. Added. Furthermore, it heated up to the temperature of 100-110 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. After removing hydrotalcite from the obtained reaction solution by filtration, the hydrotalcite was washed with toluene to obtain 1606.6 g of a vinylbenzylated solution (A-1) of 2,7-dihydroxynaphthalene. . The solid content yield was 78.5%, the solid content was 13.5%, and the hydroxyl group equivalent was 144.5 g / eq. A GPC chart of the resulting vinylbenzylated solution (A-1) is shown in FIG.
得られたビニルベンジル化物溶液(A−1)のFD‐MSのスペクトルを図2に示す。2,7‐ジヒドロキシナフタレン(Mw:160)にビニルベンジル基(Mw:116)が1個付加したピーク(M+=276)、ビニルベンジル基(Mw:116)が2個付加したピーク(M+=392)、ビニルベンジル基(Mw:116)が3個付加したピーク(M+=508)が検出された。 FIG. 2 shows the FD-MS spectrum of the resulting vinylbenzylated solution (A-1). 2,7-dihydroxynaphthalene (Mw: 160) the vinylbenzyl group (Mw: 116) is one additional peaks (M + = 276), vinylbenzyl group (Mw: 116) Two additional peaks (M + = 392), a peak (M + = 508) with three vinylbenzyl groups (Mw: 116) added was detected.
したがって、2,7‐ジヒドロキシナフタレン1モルにビニルベンジル基が1〜3モル結合した化合物であることが確認された。 Therefore, it was confirmed that the compound was obtained by bonding 1 to 3 mol of vinylbenzyl group to 1 mol of 2,7-dihydroxynaphthalene.
また、2,7‐ジヒドロキシナフタレン1モルにクロロメチルスチレン1モル全量が水酸基に反応した場合、理論水酸基当量は276g/eqとなる。一方、2,7−ジヒドロキシナフタレン1モルの芳香核側にクロロメチルスチレン1モル全量が反応した場合、理論水酸基当量が138g/eqとなる。ビニルベンジル化物(A−1)の実測水酸基当量は138g/eqに近いことから、クロロメチルスチレンの大部分が芳香核側に付加していることが確認された。 Further, when 1 mol of 2,7-dihydroxynaphthalene reacts with 1 mol of chloromethylstyrene in total with a hydroxyl group, the theoretical hydroxyl equivalent is 276 g / eq. On the other hand, when 1 mol of chloromethylstyrene is reacted with the aromatic nucleus side of 1 mol of 2,7-dihydroxynaphthalene, the theoretical hydroxyl equivalent is 138 g / eq. Since the measured hydroxyl equivalent of vinylbenzylated product (A-1) was close to 138 g / eq, it was confirmed that most of chloromethylstyrene was added to the aromatic nucleus side.
(参考例2)
窒素ガス導入管、温度計および撹拌機を備えた四口の2Lフラスコに、1,6‐ジヒドロキシナフタレン160.2g、ハイドロタルサイト(協和化学工業社製「KW‐500SH)311.0g、およびトルエン1251.3gを仕込み、60〜70℃に昇温した。次いで、クロロメチルスチレン152.6g(AGCセイミケミカル社製「CMS‐P」)を炭酸ガスによる急激な発泡に注意しながら、滴下して添加した。さらに、100〜110℃の温度に昇温して、炭酸ガスおよび水を系外へ排出しながら5時間反応させた。得られた反応溶液からハイドロタルサイトを濾過して取り除いた後、トルエンでハイドロタルサイトを洗浄することで、1,6‐ジヒドロキシナフタレンのビニルベンジル化物溶液(A−2)1646.1gを得た。固形分収率79.0%、固形分13.3%、水酸基当量は150.1g/eqであった。
(Reference Example 2)
In a four-necked 2 L flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 160.2 g of 1,6-dihydroxynaphthalene, 311.0 g of hydrotalcite (“KW-500SH” manufactured by Kyowa Chemical Industry Co., Ltd.), and toluene 1251.3 g was charged and the temperature was raised to 60 to 70 ° C. Next, 152.6 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was dropped while paying attention to rapid foaming by carbon dioxide gas. Added. Furthermore, it heated up to the temperature of 100-110 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. After removing hydrotalcite from the obtained reaction solution by filtration, the hydrotalcite was washed with toluene to obtain 1646.1 g of 1,6-dihydroxynaphthalene vinylbenzylated solution (A-2). . The solid content yield was 79.0%, the solid content was 13.3%, and the hydroxyl group equivalent was 150.1 g / eq.
(参考例3)
窒素ガス導入管、温度計および撹拌機を備えた四口の2Lフラスコに、1,6‐ジヒドロキシナフタレン208.3g、ハイドロタルサイト(協和化学工業社製「KW‐500SH)412.2g、およびメチルイソブチルケトン948.9gを仕込み、60〜70℃に昇温した。次いで、クロロメチルスチレン198.4g(AGCセイミケミカル社製「CMS‐P」)を炭酸ガスによる急激な発泡に注意しながら、滴下して添加した。さらに、100〜115℃の温度に昇温して、炭酸ガスおよび水を系外へ排出しながら5時間反応させた。得られた反応溶液からハイドロタルサイトを濾過して取り除いた後、メチルイソブチルケトンでハイドロタルサイトを洗浄することで、1,6‐ジヒドロキシナフタレンのビニルベンジル化物溶液(A−3)1401.4gを得た。固形分収率83.1%、固形分21.3%、水酸基当量153.7g/eqであった。
(Reference Example 3)
To a four-necked 2 L flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 208.3 g of 1,6-dihydroxynaphthalene, 412.2 g of hydrotalcite (“KW-500SH” manufactured by Kyowa Chemical Industry Co., Ltd.), and methyl 948.9 g of isobutyl ketone was charged, and the temperature was raised to 60 to 70 ° C. Next, 198.4 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was added dropwise while paying attention to rapid foaming by carbon dioxide gas. And added. Furthermore, it heated up to the temperature of 100-115 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. After removing hydrotalcite from the obtained reaction solution by filtration, the hydrotalcite was washed with methyl isobutyl ketone, whereby 1401.4 g of a vinylbenzylated solution of 1,6-dihydroxynaphthalene (A-3) was obtained. Obtained. The solid content yield was 83.1%, the solid content was 21.3%, and the hydroxyl group equivalent was 153.7 g / eq.
(参考例4)
窒素ガス導入管、温度計および撹拌機を備えた四口の2Lフラスコに、1,6‐ジヒドロキシナフタレン128.2g、ハイドロタルサイト(協和化学工業社製「KW‐500SH)157.0g、およびメチルイソブチルケトン385.4gを仕込み、60〜70℃に昇温した。次いで、クロロメチルスチレン79.4g(AGCセイミケミカル社製「CMS‐P」)を炭酸ガスによる急激な発泡に注意しながら、滴下して添加した。さらに、100〜115℃の温度に昇温して、炭酸ガスおよび水を系外へ排出しながら5時間反応させた。得られた反応溶液からハイドロタルサイトを濾過して取り除いた後、メチルイソブチルケトンでハイドロタルサイトを洗浄することで、1,6‐ジヒドロキシナフタレンのビニルベンジル化物溶液(A−4)665.5gを得た。固形分収率92.8%、固形分26.3%、水酸基当量127.3g/eqであった。
(Reference Example 4)
In a four-necked 2 L flask equipped with a nitrogen gas introduction tube, a thermometer and a stirrer, 128.2 g of 1,6-dihydroxynaphthalene, 157.0 g of hydrotalcite (“KW-500SH” manufactured by Kyowa Chemical Industry Co., Ltd.), and methyl 385.4 g of isobutyl ketone was charged, and the temperature was raised to 60 to 70 ° C. Next, 79.4 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was dropped while paying attention to sudden foaming by carbon dioxide gas. And added. Furthermore, it heated up to the temperature of 100-115 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. Hydrotalcite was removed by filtration from the resulting reaction solution, and then hydrotalcite was washed with methyl isobutyl ketone to obtain 665.5 g of 1,6-dihydroxynaphthalene vinylbenzylated solution (A-4). Obtained. The solid content yield was 92.8%, the solid content was 26.3%, and the hydroxyl group equivalent was 127.3 g / eq.
(参考例5)
窒素ガス導入管、温度計および撹拌機を備えた四口の300mLフラスコに、ビニルベンジル化物溶液(A−1)190.0g、1‐ナフトール20.9g、およびテトラn‐ブチルアンモニウムブロマイド0.6gを仕込み室温で溶解した。次いで、イソフタル酸クロライド32.5gを仕込み溶解し、20%水酸化ナトリウム水溶液64.1gを20〜60℃の範囲内の温度で滴下した後、50〜60℃の温度で6時間反応させた。さらに、静置して分離した水層を排出した後、純水でpHが中性になるまで洗浄した。その後、減圧留去で濃縮して、固形分67.7%、理論官能基当量209g/eqのビニル基含有の活性エステル樹脂溶液(B−1)を得た。得られたビニル基含有活性エステル樹脂溶液(B−1)のGPCチャートを図3に示す。
(Reference Example 5)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 190.0 g of vinylbenzylated solution (A-1), 20.9 g of 1-naphthol, and 0.6 g of tetra n-butylammonium bromide Was dissolved at room temperature. Next, 32.5 g of isophthalic acid chloride was charged and dissolved, and 64.1 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 60 ° C., and then reacted at a temperature of 50 to 60 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, the resultant was concentrated by distillation under reduced pressure to obtain a vinyl group-containing active ester resin solution (B-1) having a solid content of 67.7% and a theoretical functional group equivalent of 209 g / eq. A GPC chart of the resulting vinyl group-containing active ester resin solution (B-1) is shown in FIG.
得られたビニル基含有活性エステル樹脂溶液(B−1)のFD‐MSのスペクトルを図4に示す。下記一般式(9)において、i=0に相当するピーク(M+=418)、i=1、j=1に相当するピーク(M+=824)が検出された。
(参考例6)
窒素ガス導入管、温度計および撹拌機を備えた四口の300mLフラスコに、ビニルベンジル化物溶液(A−2)190.0g、1‐ナフトール19.8g、およびテトラn‐ブチルアンモニウムブロマイド0.6gを仕込み室温で溶解した。次いで、イソフタル酸クロライド30.8gを仕込み溶解し、20%水酸化ナトリウム水溶液60.7gを20〜60℃の範囲内の温度で滴下した後、50〜60℃の温度で6時間反応させた。さらに、静置して分離した水層を排出した後、純水でpHが中性になるまで洗浄した。その後、減圧留去で濃縮して、固形分65.2%、理論官能基当量212g/eqのビニル基含有の活性エステル樹脂溶液(B−2)を得た。
(Reference Example 6)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 190.0 g of vinylbenzylated solution (A-2), 19.8 g of 1-naphthol, and 0.6 g of tetra-n-butylammonium bromide Was dissolved at room temperature. Next, 30.8 g of isophthalic acid chloride was charged and dissolved, and 60.7 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 60 ° C., and then reacted at a temperature of 50 to 60 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, the resultant was concentrated by distillation under reduced pressure to obtain a vinyl group-containing active ester resin solution (B-2) having a solid content of 65.2% and a theoretical functional group equivalent of 212 g / eq.
(参考例7)
窒素ガス導入管、温度計および撹拌機を備えた四口の2Lフラスコに、ビニルベンジル化物溶液(A−3)400.0g、1‐ナフトール120.0g、およびメチルイソブチルケトン233.4gを仕込み室温で溶解した。次いで、イソフタル酸クロライド140.2gを仕込み溶解し、20%水酸化ナトリウム水溶液290.0gを20〜40℃の範囲内の温度で滴下した後、30〜40℃の温度で6時間反応させた。さらに、静置して分離した水層を排出した後、純水でpHが中性になるまで洗浄した。その後、シクロヘキサノン158.9gを徐々に添加しながらメチルイソブチルケトンを減圧留去して、固形分61.3%、理論官能基当量213g/eqのビニル基含有の活性エステル樹脂溶液(B−3)を得た。
(Reference Example 7)
A four-necked 2 L flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer was charged with 400.0 g of vinylbenzylated solution (A-3), 120.0 g of 1-naphthol, and 233.4 g of methyl isobutyl ketone. And dissolved. Next, 140.2 g of isophthalic acid chloride was charged and dissolved, and 290.0 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 40 ° C., and then reacted at a temperature of 30 to 40 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, methyl isobutyl ketone was distilled off under reduced pressure while gradually adding 158.9 g of cyclohexanone, and a vinyl group-containing active ester resin solution (B-3) having a solid content of 61.3% and a theoretical functional group equivalent of 213 g / eq. Got.
(参考例8)
窒素ガス導入管、温度計および撹拌機を備えた四口の300mLフラスコに、ビニルベンジル化物溶液(A−4)40.0g、1‐ナフトール22.1g、およびメチルイソブチルケトン50.8gを仕込み室温で溶解した。次いで、イソフタル酸クロライド23.7gを仕込み溶解し、20%水酸化ナトリウム水溶液49.1gを20〜40℃の範囲内の温度で滴下した後、30〜40℃の温度で6時間反応させた。さらに、静置して分離した水層を排出した後、純水でpHが中性になるまで洗浄した。その後、シクロヘキサノン25.8gを徐々に添加しながらメチルイソブチルケトンを減圧留去して、固形分79.1%、理論官能基当量205g/eqのビニル基含有の活性エステル樹脂溶液(B−4)を得た。
(Reference Example 8)
A four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 40.0 g of vinylbenzylated solution (A-4), 22.1 g of 1-naphthol, and 50.8 g of methyl isobutyl ketone at room temperature. And dissolved. Next, 23.7 g of isophthalic acid chloride was charged and dissolved, and 49.1 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 40 ° C., and then reacted at a temperature of 30 to 40 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, methyl isobutyl ketone was distilled off under reduced pressure while gradually adding 25.8 g of cyclohexanone to give a vinyl group-containing active ester resin solution (B-4) having a solid content of 79.1% and a theoretical functional group equivalent of 205 g / eq. Got.
(実施例1)1,1’‐メチレンビス(2‐ナフトール)のビニルベンジル化
窒素ガス導入管、温度計、撹拌機を備えた四口の500mLフラスコに、1,1’‐メチレンビス(2‐ナフトール)75.8g、ハイドロタルサイト(協和化学工業社製「KW‐1000」)42.9g、メチル‐n‐アミルケトン(以下「MAK」と略記する。)302.7gを仕込み、60〜70℃に昇温した。次いで、クロロメチルスチレン25.0g(AGCセイミケミカル社製「CMS‐P」)を炭酸ガスによる急激な発泡に注意しながら、滴下して添加した。さらに、120〜130℃の温度に昇温して、炭酸ガスおよび水を系外へ排出しながら5時間反応させた。得られた反応溶液からハイドロタルサイトを濾過して取り除いた後、MAKでハイドロタルサイトを洗浄することで、1,1’‐メチレンビス(2‐ナフトール)のビニルベンジル化物溶液(A−5)431.8gを得た。固形分収率94.6%、固形分20.8%、水酸基当量は201.5g/eqであった。
Example 1 Vinylbenzylation of 1,1′-methylenebis (2-naphthol) 1,1′-methylenebis (2-naphthol) was placed in a four-necked 500 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer. ) 75.8 g, hydrotalcite (“KW-1000” manufactured by Kyowa Chemical Industry Co., Ltd.) 42.9 g, methyl-n-amyl ketone (hereinafter abbreviated as “MAK”) 302.7 g, and charged at 60 to 70 ° C. The temperature rose. Next, 25.0 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was added dropwise while paying attention to rapid foaming by carbon dioxide gas. Furthermore, it heated up at the temperature of 120-130 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. After removing hydrotalcite from the obtained reaction solution by filtration, the hydrotalcite was washed with MAK, whereby a vinylbenzylated solution (A-5) 431 of 1,1′-methylenebis (2-naphthol) was obtained. .8 g was obtained. The solid content yield was 94.6%, the solid content was 20.8%, and the hydroxyl group equivalent was 201.5 g / eq.
(実施例2)ナフトールザイロック樹脂のビニルベンジル化
窒素ガス導入管、温度計、撹拌機を備えた四口の2Lフラスコに、ナフトールザイロック樹脂(新日鉄住金化学社製「SN‐485」)172.0g、ハイドロタルサイト(協和化学工業社製「KW‐1000」)125.4g、トルエン981.0gを仕込み、60〜70℃に昇温した。次いで、クロロメチルスチレン73.3g(AGCセイミケミカル社製「CMS‐P」)を炭酸ガスによる急激な発泡に注意しながら、滴下して添加した。さらに、100〜110℃の温度に昇温して、炭酸ガスおよび水を系外へ排出しながら5時間反応させた。得られた反応溶液からハイドロタルサイトを濾過して取り除いた後、トルエンでハイドロタルサイトを洗浄することで、ナフトールザイロック樹脂のビニルベンジル化物溶液(A−6)1223.9gを得た。固形分収率92.7%、固形分17.3%、水酸基当量は289.2g/eqであった。得られたビニルベンジル化物溶液(A−6)のGPCチャートを図5に示す。
(Example 2) Vinyl benzylation of naphthol zylock resin A naphthol zylock resin ("SN-485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 172 was added to a four-necked 2L flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer. 0.04 g, hydrotalcite (“KW-1000” manufactured by Kyowa Chemical Industry Co., Ltd.) 125.4 g and toluene 981.0 g were charged, and the temperature was raised to 60 to 70 ° C. Subsequently, 73.3 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was added dropwise while paying attention to rapid foaming with carbon dioxide gas. Furthermore, it heated up to the temperature of 100-110 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. Hydrotalcite was removed by filtration from the resulting reaction solution, and then the hydrotalcite was washed with toluene to obtain 1223.9 g of a vinyl benzylated solution (A-6) of naphthol zylock resin. The solid content yield was 92.7%, the solid content was 17.3%, and the hydroxyl group equivalent was 289.2 g / eq. A GPC chart of the resulting vinylbenzylated solution (A-6) is shown in FIG.
得られたビニルベンジル化物溶液(A−6)のFD‐MSのスペクトルを図6に示す。下記一般式(10)において、q=0、r=0、s=1に相当するピーク(M+=390)、q=1、r=0、s=1に相当するピーク(M+=506)、q=1、r=1、s=1に相当するピーク(M+=622)が検出された。
(実施例3)1,1’‐メチレンビス(2‐ナフトール)のビニルベンジル化物のエステル化物
窒素ガス導入管、温度計、撹拌機を備えた四口の300mLフラスコに、ビニルベンジル化物溶液(A−5)200.0g、1‐ナフトール36.4g、テトラn‐ブチルアンモニウムブロマイド0.6gを仕込み室温で溶解した。次いで、イソフタル酸クロライド46.5gを仕込み溶解し、20%水酸化ナトリウム水溶液91.7gを20〜40℃の範囲内の温度で滴下した後、50〜60℃の温度で6時間反応させた。さらに、静置して分離した水層を排出した後、純水でpHが中性になるまで洗浄した。その後、減圧留去で濃縮して、固形分72.0%、理論官能基当量235g/eqのビニル基含有の活性エステル樹脂溶液(B−5)を得た。
Example 3 Esterified product of 1,1′-methylenebis (2-naphthol) vinylbenzylated product A vinylbenzylated solution (A−) was added to a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer. 5) 200.0 g, 1-naphthol 36.4 g and tetra n-butylammonium bromide 0.6 g were charged and dissolved at room temperature. Next, 46.5 g of isophthalic acid chloride was charged and dissolved, and 91.7 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 40 ° C., and then reacted at a temperature of 50 to 60 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, the resultant was concentrated by distillation under reduced pressure to obtain a vinyl group-containing active ester resin solution (B-5) having a solid content of 72.0% and a theoretical functional group equivalent of 235 g / eq.
(実施例4)ナフトールザイロック樹脂のビニルベンジル化物のエステル化物
窒素ガス導入管、温度計、撹拌機を備えた四口の500mLフラスコに、ビニルベンジル化物溶液(A−6)250.0g、1‐ナフトール39.9g、テトラn‐ブチルアンモニウムブロマイド0.7gを仕込み室温で溶解した。次いで、イソフタル酸クロライド43.3gを仕込み溶解し、20%水酸化ナトリウム水溶液83.5gを20〜40℃の範囲内の温度で滴下した後、50〜60℃の温度で6時間反応させた。さらに、静置して分離した水層を排出した後、純水でpHが中性になるまで洗浄した。その後、減圧留去で濃縮して、固形分69.5%、理論官能基当量260g/eqのビニル基含有の活性エステル樹脂溶液(B−6)を得た。得られたビニル基含有活性エステル樹脂溶液(B−6)のGPCチャートを図7に示す。
(Example 4) Esterified product of vinyl benzylated product of naphthol zylock resin In a four-necked 500 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 250.0 g of vinyl benzylated solution (A-6), 1 -39.9 g of naphthol and 0.7 g of tetra n-butylammonium bromide were charged and dissolved at room temperature. Next, 43.3 g of isophthalic acid chloride was charged and dissolved, 83.5 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 40 ° C., and then reacted at a temperature of 50 to 60 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, the resultant was concentrated by distillation under reduced pressure to obtain a vinyl group-containing active ester resin solution (B-6) having a solid content of 69.5% and a theoretical functional group equivalent of 260 g / eq. The GPC chart of the obtained vinyl group-containing active ester resin solution (B-6) is shown in FIG.
(比較例1)
窒素ガス導入管、温度計および撹拌機を備えた四口の300mLフラスコに、1‐ナフトール36.1g、イソフタル酸クロライド25.3g、およびトルエン183.5gを仕込み、室温で溶解した。次いで、20%水酸化ナトリウム水溶液52.0gを20〜60℃の範囲内の温度で滴下した後、50〜60℃の温度で6時間反応させた。その後、反応液を室温まで冷却して、析出した結晶を濾過して回収した。さらに、得られた結晶を純水で洗浄した後、80℃で減圧乾燥し、ジメチルアセトアミドに溶解して固形分30%の活性エステル化合物溶液(B−7)を得た。理論官能基当量は209g/eqであった。
(Comparative Example 1)
A 4-neck 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 1-naphthol (36.1 g), isophthalic acid chloride (25.3 g), and toluene (183.5 g) and dissolved at room temperature. Next, 52.0 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 60 ° C, and then reacted at a temperature of 50 to 60 ° C for 6 hours. Thereafter, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration. Further, the obtained crystal was washed with pure water, dried under reduced pressure at 80 ° C., and dissolved in dimethylacetamide to obtain an active ester compound solution (B-7) having a solid content of 30%. The theoretical functional group equivalent was 209 g / eq.
(比較例2)
ビフェニルアラルキルフェノール樹脂(エア・ウォーター社製「HE200C−17」、150℃でのICI粘度150mPa・s、水酸基当量210g/eq)をメチルエチルケトン(MEK)に溶解して固形分60%の樹脂溶液(B−8)とした。
(Comparative Example 2)
Biphenylaralkylphenol resin (“HE200C-17” manufactured by Air Water, ICI viscosity at 150 ° C. 150 mPa · s, hydroxyl group equivalent 210 g / eq) is dissolved in methyl ethyl ketone (MEK) to obtain a resin solution (B −8).
(参考例9〜12、実施例5および6ならびに比較例3および4)
参考例5〜8、実施例3および4ならびに比較例1および2において製造した樹脂溶液(B−1〜B−8)のそれぞれに、ビフェニルアラルキル型エポキシ樹脂(日本化薬社製「NC−3000H」、エポキシ当量290g/eq)の固形分75%のメチルエチルケトン(MEK)溶液、およびジメチルアミノピリジン(DMAP)を混合し、樹脂組成物ワニスを作製した。各樹脂組成物ワニスを製造するための配合量は表1に記載のとおり(表1中の配合量の数値は質量部を意味する。)であった。銅箔光沢面に各樹脂組成物ワニスを塗工し、100℃で8分間乾燥し、200℃で6時間硬化させた。硬化後、銅箔から引き剥がして膜厚約80μmの硬化物フィルム(硬化物)を得た。
(Reference Examples 9 to 12, Examples 5 and 6 and Comparative Examples 3 and 4)
In each of the resin solutions (B-1 to B-8) produced in Reference Examples 5 to 8, Examples 3 and 4 and Comparative Examples 1 and 2, a biphenylaralkyl epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd.) was used. ”, A methyl ethyl ketone (MEK) solution having an epoxy equivalent of 290 g / eq) having a solid content of 75%, and dimethylaminopyridine (DMAP) were mixed to prepare a resin composition varnish. The compounding amount for producing each resin composition varnish was as shown in Table 1 (the numerical value of the compounding amount in Table 1 means part by mass). Each resin composition varnish was applied to the glossy surface of the copper foil, dried at 100 ° C. for 8 minutes, and cured at 200 ° C. for 6 hours. After curing, it was peeled off from the copper foil to obtain a cured film (cured product) having a film thickness of about 80 μm.
(ガラス転移温度Tgの測定)
参考例9〜12、実施例5および6ならびに比較例3および4で得られた硬化物フィルムを、所定の大きさにカット(切り出)してガラス転移温度測定のサンプルとした。以下の条件にてサンプルのガラス転移温度Tgを測定した。
測定機器:リガク社製熱機械分析装置「TMA8310evo」
サンプル寸法:幅5mm×長さ15mm×厚さ0.080mm(80μm)
雰囲気:窒素中
測定温度:25〜300℃
昇温速度:10℃/分
測定モ−ド:引張
(Measurement of glass transition temperature Tg)
The cured product films obtained in Reference Examples 9 to 12, Examples 5 and 6 and Comparative Examples 3 and 4 were cut (cut out) to a predetermined size to obtain glass transition temperature measurement samples. The glass transition temperature Tg of the sample was measured under the following conditions.
Measuring instrument: Rigaku's thermomechanical analyzer "TMA8310evo"
Sample dimensions: width 5 mm x length 15 mm x thickness 0.080 mm (80 μm)
Atmosphere: In nitrogen Measurement temperature: 25-300 ° C
Temperature increase rate: 10 ° C / min Measurement mode: Tensile
(誘電特性の評価)
参考例9〜12、実施例5および6ならびに比較例3および4で得られた硬化物フィルムを所定の大きさに切り出して、測定用のサンプルとした。下記の測定機器を用いて、以下の条件にてサンプルの誘電特性を測定した。
測定機器:キーサイトテクノロジー社製「ネットワークアナライザーE5071C」
関東電子応用開発社製空洞共振器摂動法誘電率測定装置
周波数:1GHz
サンプル寸法:幅2mm×長さ100mm×厚さ0.080mm(80μm)
(Evaluation of dielectric properties)
The cured product films obtained in Reference Examples 9 to 12, Examples 5 and 6 and Comparative Examples 3 and 4 were cut into a predetermined size and used as measurement samples. The dielectric properties of the samples were measured using the following measuring equipment under the following conditions.
Measuring equipment: “Network Analyzer E5071C” manufactured by Keysight Technology
Cavity resonator perturbation method dielectric constant measuring device manufactured by Kanto Electronics Application Development Company Frequency: 1 GHz
Sample dimensions: width 2 mm x length 100 mm x thickness 0.080 mm (80 μm)
評価結果を表1に示す。表1に示されるように、本発明の構成を備えるビニルベンジル化フェノール化合物(実施例1および2)を用いて製造された活性エステル樹脂(実施例1および2)を含む樹脂組成物ワニス(実施例5および6)から得られた硬化フィルム(実施例5および6)は、参考例に係る硬化フィルム(参考例9〜12)に比べて、誘電正接が低い。 The evaluation results are shown in Table 1. As shown in Table 1, a resin composition varnish containing active ester resins (Examples 1 and 2) produced using vinylbenzylated phenolic compounds (Examples 1 and 2) having the structure of the present invention (Examples) The cured films obtained from Examples 5 and 6) (Examples 5 and 6) have a lower dielectric loss tangent than the cured films according to Reference Examples (Reference Examples 9 to 12).
Claims (14)
単環または多環の芳香核を2個以上有する2官能フェノール化合物およびビニルベンジルハライド化合物を、ハイドロタルサイト類を脱ハロゲン化水素剤として反応させること
を特徴とするビニルベンジル化フェノール化合物の製造方法。 A method for producing a vinylbenzylated phenol compound according to claim 1, comprising:
A method for producing a vinylbenzylated phenol compound, comprising reacting a bifunctional phenol compound having two or more monocyclic or polycyclic aromatic nuclei and a vinylbenzyl halide compound with hydrotalcites as a dehydrohalogenating agent .
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US15/346,422 US10252965B2 (en) | 2015-11-11 | 2016-11-08 | Vinylbenzylated phenol compound, method of manufacturing vinylbenzylated phenol compound, activated ester resin, method of manufacturing activated ester resin, thermoset resin composition, hardened material of thermoset resin composition, interlayer insulating material, prepreg, and method of manufacturing prepreg |
TW105136449A TWI629259B (en) | 2015-11-11 | 2016-11-09 | Vinyl benzylated phenol compound, method for producing the same, active ester resin and method for producing the same, thermosetting resin composition and cured product thereof, interlayer insulating material, prepreg, and method for producing the same |
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