JP6867459B2 - Curable resin composition, dry film, copper foil with resin, cured product, and electronic components - Google Patents
Curable resin composition, dry film, copper foil with resin, cured product, and electronic components Download PDFInfo
- Publication number
- JP6867459B2 JP6867459B2 JP2019179638A JP2019179638A JP6867459B2 JP 6867459 B2 JP6867459 B2 JP 6867459B2 JP 2019179638 A JP2019179638 A JP 2019179638A JP 2019179638 A JP2019179638 A JP 2019179638A JP 6867459 B2 JP6867459 B2 JP 6867459B2
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- Prior art keywords
- epoxy resin
- compound
- nitrogen atom
- resin
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims description 85
- 239000011347 resin Substances 0.000 title claims description 85
- 239000011342 resin composition Substances 0.000 title claims description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 66
- 239000011889 copper foil Substances 0.000 title claims description 57
- 239000003822 epoxy resin Substances 0.000 claims description 140
- 229920000647 polyepoxide Polymers 0.000 claims description 140
- 150000001875 compounds Chemical class 0.000 claims description 78
- 229910052757 nitrogen Inorganic materials 0.000 claims description 75
- 125000004185 ester group Chemical group 0.000 claims description 71
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 71
- 239000007787 solid Substances 0.000 claims description 42
- 239000011256 inorganic filler Substances 0.000 claims description 36
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 125000003700 epoxy group Chemical group 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 239000004305 biphenyl Substances 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 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- -1 ester compound Chemical class 0.000 description 70
- 239000010410 layer Substances 0.000 description 55
- 239000000047 product Substances 0.000 description 49
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 32
- 238000000034 method Methods 0.000 description 29
- 238000001723 curing Methods 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000002245 particle Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 22
- 229920001187 thermosetting polymer Polymers 0.000 description 19
- 239000002904 solvent Substances 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 14
- 239000004020 conductor Substances 0.000 description 14
- 150000002989 phenols Chemical class 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 12
- 235000019445 benzyl alcohol Nutrition 0.000 description 12
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 235000013824 polyphenols Nutrition 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 229920005992 thermoplastic resin Polymers 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000003377 acid catalyst Substances 0.000 description 7
- 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 7
- 239000007822 coupling agent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 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 7
- 239000005011 phenolic resin Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 5
- 239000013034 phenoxy resin Substances 0.000 description 5
- 229920006287 phenoxy resin Polymers 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- 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 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 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 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 229920003319 Araldite® Polymers 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004962 Polyamide-imide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000011354 acetal resin Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 3
- 125000004957 naphthylene group Chemical group 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920002312 polyamide-imide Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
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- 229920002223 polystyrene Polymers 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 2
- 125000005978 1-naphthyloxy group Chemical group 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
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
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- 239000001431 2-methylbenzaldehyde Substances 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
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- 229920001296 polysiloxane Polymers 0.000 description 1
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- 239000011164 primary particle Substances 0.000 description 1
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- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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- NNENFOSYDBTCBO-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC NNENFOSYDBTCBO-UHFFFAOYSA-M 0.000 description 1
- QEXITCCVENILJI-UHFFFAOYSA-M tributyl(phenyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)C1=CC=CC=C1 QEXITCCVENILJI-UHFFFAOYSA-M 0.000 description 1
- GLSQMJPVEVGXMZ-UHFFFAOYSA-N tributyl-(2,5-dihydroxyphenyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)C1=CC(O)=CC=C1O GLSQMJPVEVGXMZ-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
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- 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
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Description
本発明は、硬化性樹脂組成物、ドライフィルム、樹脂付き銅箔、硬化物、及び電子部品に関し、特にエポキシ樹脂を含む熱硬化性の硬化性樹脂組成物、ドライフィルム、樹脂付き銅箔、硬化物、及び電子部品に関する。 The present invention relates to a curable resin composition, a dry film, a copper foil with a resin, a cured product, and an electronic component, and particularly a thermosetting curable resin composition containing an epoxy resin, a dry film, a copper foil with a resin, and a cured product. Regarding things and electronic parts.
プリント配線板などの電子部品を形成する絶縁材料として、従来よりエポキシ樹脂を含有する熱硬化性樹脂組成物が用いられており、通常、硬化物に様々な特性を付与するために、種々の硬化剤がエポキシ樹脂と併用されている。
例えば、特許文献1は、エポキシ樹脂と、硬化剤としての活性エステル化合物及びトリアジン含有フェノール樹脂と、マレイミド化合物と、フェノキシ化合物と、を含むエポキシ樹脂組成物を開示する。特許文献1のエポキシ樹脂組成物によれば、得られた硬化物はめっき導体に対する高い密着力を示し、線膨張率が低い絶縁層を達成し得ることが開示されている。
A thermosetting resin composition containing an epoxy resin has been conventionally used as an insulating material for forming an electronic component such as a printed wiring board, and usually, in order to impart various properties to the cured product, various curing methods have been used. The agent is used in combination with epoxy resin.
For example, Patent Document 1 discloses an epoxy resin composition containing an epoxy resin, an active ester compound as a curing agent, a triazine-containing phenol resin, a maleimide compound, and a phenoxy compound. According to the epoxy resin composition of Patent Document 1, it is disclosed that the obtained cured product exhibits high adhesion to the plated conductor and can achieve an insulating layer having a low coefficient of linear expansion.
しかし、電子部品の絶縁層形成用の硬化性樹脂組成物には、めっき導体に対する高い密着性等のほか、信頼性の観点からその硬化物に高い耐熱性を付与することも求められる。さらに、近年、高速通信の採用、すなわち、高周波化に伴い、伝送損失が増加傾向にあるため、電子部品の絶縁材料には伝送損失を抑制することができる低誘電正接化が要求されている。
しかし、従来の硬化性樹脂組成物により各特性の何れか一つを向上させることは比較的容易だが、全ての特性をまんべんなく向上させることは困難である。例えば、エポキシ樹脂は硬化物の強度やめっき導体に対する高い密着性に寄与する成分であるが、エポキシ樹脂の配合量によっては硬化物の誘電正接を増加させてしまったり、めっき導体に対する密着性が低下するなど、それらの特性を同時に満足させることが困難になることが発明者らの検討によりわかってきている。
前記課題を鑑みた本発明の目的は、高い耐熱性、低誘電正接、及び導体に対する高い密着性を備えた硬化物が得られる熱硬化性樹脂組成物、該組成物から得られる樹脂層を有するドライフィルム、樹脂付き銅箔、硬化物、及び電子部品を提供することにある。
However, the curable resin composition for forming an insulating layer of an electronic component is required to impart high heat resistance to the cured product from the viewpoint of reliability as well as high adhesion to a plated conductor. Further, in recent years, with the adoption of high-speed communication, that is, with the increase in high frequency, the transmission loss tends to increase, so that the insulating material of electronic components is required to have a low dielectric loss tangent capable of suppressing the transmission loss.
However, although it is relatively easy to improve any one of the properties with the conventional curable resin composition, it is difficult to evenly improve all the properties. For example, epoxy resin is a component that contributes to the strength of the cured product and high adhesion to the plated conductor, but depending on the amount of epoxy resin blended, the dielectric loss tangent of the cured product may increase or the adhesion to the plated conductor may decrease. It has become clear from the studies of the inventors that it becomes difficult to satisfy these characteristics at the same time.
An object of the present invention in view of the above problems is to have a thermosetting resin composition capable of obtaining a cured product having high heat resistance, low dielectric loss tangent, and high adhesion to a conductor, and a resin layer obtained from the composition. The purpose of the present invention is to provide dry films, copper foils with resins, cured products, and electronic components.
本発明の目的は、(A)窒素原子を含むエポキシ樹脂と、
(B)窒素原子を含まないエポキシ樹脂と、
(C)活性エステル基を有する化合物と、
(D)無機フィラーと、
を含有する硬化性樹脂組成物であって、
(A)窒素原子を含むエポキシ樹脂および(B)窒素原子を含まないエポキシ樹脂におけるエポキシ基の総量の、(C)活性エステル基を有する化合物におけるエステル基の総量に対する比が0.2〜0.6であることを特徴とする硬化性樹脂組成物により達成されることが見出された。
本発明の硬化性樹脂組成物で用いられる(C)活性エステル基を有する化合物は、下記一般式(1)
下記一般式(2):
mは1〜6の整数であり、nはそれぞれ独立的に1〜5の整数であり、qはそれぞれ独立的に1〜6の整数であり、
式(3)中、kはそれぞれ独立的に1〜5の整数であり、
式(4)中、Yは上記式(3)で表される基(kはそれぞれ独立的に1〜5の整数)であり、tはそれぞれ独立的に0〜5の整数である)
で表される構造部位を有し、その両末端が一価のアリールオキシ基である構造を有する化合物であることが好ましい。
さらに、本発明の目的は、上記硬化性樹脂組成物を樹脂層として有することを特徴とするドライフィルム、
銅箔またはキャリア付き銅箔上に、上記の硬化性樹脂組成物を樹脂層として有することを特徴とする樹脂付き銅箔、
上記硬化性樹脂組成物、ドライフィルムの樹脂層、又は樹脂付き銅箔の樹脂層の硬化物、および
上記の硬化物を有することを特徴とする電子部品によっても、それぞれ達成される。
An object of the present invention is (A) an epoxy resin containing a nitrogen atom and
(B) Epoxy resin containing no nitrogen atom and
(C) A compound having an active ester group and
(D) Inorganic filler and
A curable resin composition containing
The ratio of the total amount of epoxy groups in (A) an epoxy resin containing a nitrogen atom and (B) an epoxy resin containing no nitrogen atom to the total amount of ester groups in a compound having an active ester group is 0.2 to 0. It has been found that this is achieved with a curable resin composition characterized by being 6.
The compound having an active ester group (C) used in the curable resin composition of the present invention has the following general formula (1).
m is an integer of 1 to 6, n is an integer of 1 to 5 independently, and q is an integer of 1 to 6 independently.
In equation (3), k is an integer of 1 to 5 independently.
In the formula (4), Y is a group represented by the above formula (3) (k is an integer of 1 to 5 independently), and t is an integer of 0 to 5 independently).
It is preferable that the compound has a structure site represented by and has a structure in which both ends thereof are monovalent aryloxy groups.
Furthermore, an object of the present invention is a dry film, characterized in that the curable resin composition is provided as a resin layer.
A copper foil with a resin, which comprises the above-mentioned curable resin composition as a resin layer on a copper foil or a copper foil with a carrier.
It is also achieved by the above-mentioned curable resin composition, the cured product of the resin layer of the dry film, or the cured product of the resin layer of the copper foil with resin, and the electronic component characterized by having the above-mentioned cured product.
本発明の硬化性樹脂組成物によれば、得られた硬化物は高い耐熱性、低誘電正接、及び導体に対する高い密着性を兼ね備えたものとなる。また、本発明の硬化性樹脂組成物から得られる樹脂層を有するドライフィルム、本発明の硬化性樹脂組成物から得られる樹脂層を有する樹脂付き銅箔、本発明の硬化性樹脂組成物、ドライフィルムの樹脂層または樹脂付き銅箔の樹脂層の硬化物、この硬化物を有する電子部品についても、それぞれ同様に高い耐熱性、低誘電正接、及び導体に対する高い密着性を兼ね備えたものとなる。 According to the curable resin composition of the present invention, the obtained cured product has high heat resistance, low dielectric loss tangent, and high adhesion to a conductor. Further, a dry film having a resin layer obtained from the curable resin composition of the present invention, a copper foil with a resin having a resin layer obtained from the curable resin composition of the present invention, a curable resin composition of the present invention, and a dry film. The cured product of the resin layer of the film or the resin layer of the copper foil with resin, and the electronic component having this cured product also have high heat resistance, low dielectric adduct, and high adhesion to the conductor, respectively.
<硬化性樹脂組成物>
本発明の硬化性樹脂組成物は、
(A)窒素原子を含むエポキシ樹脂(A成分ともいう)と、
(B)窒素原子を含まないエポキシ樹脂(B成分ともいう)と、
(C)活性エステル基を有する化合物(C成分ともいう)と、
(D)無機フィラー(D成分ともいう)と、を含有し、
(A)窒素原子を含むエポキシ樹脂および(B)窒素原子を含まないエポキシ樹脂におけるエポキシ基の総量の、(C)活性エステル基を有する化合物におけるエステル基の総量に対する比が0.2〜0.6であることを特徴とするものである。
<Curable resin composition>
The curable resin composition of the present invention is
(A) Epoxy resin containing a nitrogen atom (also referred to as component A) and
(B) Epoxy resin (also called B component) that does not contain nitrogen atoms,
(C) A compound having an active ester group (also referred to as C component) and
(D) Inorganic filler (also referred to as D component) and
The ratio of the total amount of epoxy groups in (A) an epoxy resin containing a nitrogen atom and (B) an epoxy resin containing no nitrogen atom to the total amount of ester groups in a compound having an active ester group is 0.2 to 0. It is characterized by being 6.
上述のエポキシ基の総量とは、(i)組成物中に含まれる(A)窒素原子を含むエポキシ樹脂の配合量を、(A)窒素原子を含むエポキシ樹脂のエポキシ当量で除した値と、(ii)組成物中に含まれる(B)窒素原子を含まないエポキシ樹脂の配合量を(B)窒素原子を含まないエポキシ樹脂のエポキシ当量で除した値と、の和である。また、(C)活性エステル基を有する化合物の活性エステル基の総量は、組成物中に含まれる(C)活性エステル基を有する化合物の配合量を、(C)活性エステル基を有する化合物の活性エステル当量で除して求めることができる。なお、A〜C成分は、それぞれ後述のようにそれぞれ複数種類の化合物を含むものであってもよいが、その場合には各化合物ごとに、配合量をエポキシ当量または活性エステル当量で除して、エポキシ基の総量またはエステル基の総量を求める。 The above-mentioned total amount of epoxy groups is a value obtained by dividing (a) the amount of the epoxy resin containing a nitrogen atom contained in the composition by (A) the epoxy equivalent of the epoxy resin containing a nitrogen atom. It is the sum of (ii) the blending amount of (B) the epoxy resin containing no nitrogen atom contained in the composition and the value obtained by dividing (B) the epoxy equivalent of the epoxy resin containing no nitrogen atom. The total amount of active ester groups of the compound having (C) active ester group is the blending amount of the compound having (C) active ester group contained in the composition, and the activity of the compound having (C) active ester group. It can be obtained by dividing by the ester equivalent. The components A to C may each contain a plurality of types of compounds as described later. In that case, the blending amount of each compound is divided by the epoxy equivalent or the active ester equivalent. , The total amount of epoxy groups or the total amount of ester groups is determined.
本発明の硬化性樹脂組成物において、A成分〜D成分を含有し、かつ、前記総量の比(A成分及びB成分中のエポキシ基の総量のエステル基の総量に対する比)が0.2〜0.6であることにより、高い耐熱性、低誘電正接、及び導体に対する高い密着性を兼ね備えた硬化物を得ることができる。
上記総量の比は、導体に対する高い密着性を有しながら、ガラス転移温度(Tg)が高く、低誘電正接の硬化物が得られることから、前記総量の比は、0.2〜0.5であることがより好ましく、0.2〜0.4であることが特に好ましい。
In the curable resin composition of the present invention, the components A to D are contained, and the ratio of the total amount (the ratio of the total amount of epoxy groups in the components A and B to the total amount of ester groups) is 0.2 to. When it is 0.6, a cured product having high heat resistance, low dielectric loss tangent, and high adhesion to a conductor can be obtained.
The ratio of the total amount is 0.2 to 0.5 because the glass transition temperature (Tg) is high and a cured product having a low dielectric loss tangent is obtained while having high adhesion to the conductor. Is more preferable, and 0.2 to 0.4 is particularly preferable.
以下に、本発明の熱硬化性樹脂組成物が含有する各成分について説明する。なお、本明細書において、数値範囲を「〜」で表記する場合、それらの数値を含む範囲(即ち、・・・以上・・・以下)を意味するものとする。 Hereinafter, each component contained in the thermosetting resin composition of the present invention will be described. In addition, in this specification, when a numerical range is expressed by "~", it means a range including those numerical values (that is, ... or more ... or less).
[(A)窒素原子を含むエポキシ樹脂]
本発明の熱硬化性樹脂組成物は、(A)窒素原子を含むエポキシ樹脂を含む。(A)窒素原子を含むエポキシ樹脂は、1個以上の窒素原子とエポキシ基を有する化合物である。その例としては、分子中に、窒素原子を1個〜4個およびエポキシ基を2個有する2官能性エポキシ樹脂、分子中に窒素原子を1個〜4個およびエポキシ基を3個以上有する多官能エポキシ樹脂等が挙げられる。なお、窒素原子を含むものであれば水素添加されたエポキシ樹脂であってもよい。
[(A) Epoxy resin containing nitrogen atom]
The thermosetting resin composition of the present invention contains (A) an epoxy resin containing a nitrogen atom. (A) The epoxy resin containing a nitrogen atom is a compound having one or more nitrogen atoms and an epoxy group. Examples are bifunctional epoxy resins having 1 to 4 nitrogen atoms and 2 epoxy groups in the molecule, and many having 1 to 4 nitrogen atoms and 3 or more epoxy groups in the molecule. Examples include functional epoxy resins. A hydrogenated epoxy resin may be used as long as it contains a nitrogen atom.
(A)窒素原子を含むエポキシ樹脂は下記(A−1)、(A−2)または(A−3)で表され、
更に、式中複数のRはそれぞれ独立的に、グリシジル基、アルキル基、または水素原子であるが、1個以上、好ましくは2個以上のRはグリシジル基である。アルキル基としては、例えば、炭素数が1以上6以下、好ましくは炭素数が1以上3以下の、直鎖状又は分岐鎖状のアルキル基が挙げられる。より具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基等が挙げられ、メチル基、エチル基であることがより好ましい。
(A)窒素原子を含むエポキシ樹脂の他の例としては、ヘテロ環骨格、例えばトリアジン骨格を有するエポキシ樹脂も含まれる。例えば、トリグリシジルイソシアヌレート(日産化学社製TEPIC−VLなどのTEPICシリーズが挙げられる。
(A) The epoxy resin containing a nitrogen atom is represented by the following (A-1), (A-2) or (A-3).
Further, each of the plurality of Rs in the formula is independently a glycidyl group, an alkyl group, or a hydrogen atom, but one or more, preferably two or more Rs are glycidyl groups. Examples of the alkyl group include a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, preferably 1 or more and 3 or less carbon atoms. More specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and the like can be mentioned, and methyl group and ethyl group can be used. More preferably.
(A) Other examples of the epoxy resin containing a nitrogen atom also include an epoxy resin having a heterocyclic skeleton, for example, a triazine skeleton. For example, a TEPIC series such as triglycidyl isocyanurate (TEPIC-VL manufactured by Nissan Chemical Industries, Ltd.) can be mentioned.
(A)窒素原子を含むエポキシ樹脂のうち、1〜4個、特に3または4個のエポキシ基を有するグリシジルアミン型エポキシ樹脂が好ましい。3官能または4官能グリシジルアミン型エポキシ樹脂の具体例としては、N,N,O−トリグリシジル−m−アミノフェノール(ハンツマン・アドバンスト・マテリアルズ社製、アラルダイト(登録商標)MY0600)、N,N,O−トリグリシジル−4−アミノ−3−メチルフェノール、N,N,N’,N’−テトラグリシジル−4,4’−メチレンジアニリン(三菱ケミカル株式会社製、jER(登録商標)604)、テトラグリシジルジアミノジフェニルメタン(ハンツマン・アドバンスト・マテリアルズ社製、アラルダイト(登録商標)MY721)N,N-ビス(オキシラニルメチル)-4-(オキシラニルメトキシ)アニリン(N,N,O−トリグリシジル−p−アミノフェノール、三菱ケミカル株式会社製、jER(登録商標)630およびJER(登録商標)630LSD、またはADEKA社製EP−3950SおよびEP−3950SL、ハンツマン・アドバンスト・マテリアルズ社製アラルダイト(登録商標)MY0500、)、N,N,N’,N’−テトラグリシジル−2,2’−ジエチル−4,4’−メチレンジアニリン、N,N,N’,N’−テトラグリシジル−m−キシリレンジアミン、
2官能グリシジルアミン型エポキシ樹脂の具体例としては、N,N−ジグリシジルアニリン、N,N−ビス(オキシラニルメチル)−2−(メチルアニリン)(N,N−ジグリシジル−o−トルイジン、ADEKA社製 EP−3980S)を挙げることができる。
このほか、エポキシ樹脂をウレタン変性した材料を(A)窒素原子を含むエポキシ樹脂として用いることも可能であり、具体例としてはADEKA社製のEPU−73Bを挙げることができる。
(A) Among the epoxy resins containing nitrogen atoms, a glycidylamine type epoxy resin having 1 to 4, particularly 3 or 4 epoxy groups is preferable. Specific examples of the trifunctional or tetrafunctional glycidylamine type epoxy resin include N, N, O-triglycidyl-m-aminophenol (manufactured by Huntsman Advanced Materials, Inc., Araldite (registered trademark) MY0600), N, N. , O-triglycidyl-4-amino-3-methylphenol, N, N, N', N'-tetraglycidyl-4,4'-methylenedianiline (manufactured by Mitsubishi Chemical Co., Ltd., jER® 604) , Tetraglycidyl diaminodiphenylmethane (manufactured by Huntsman Advanced Materials, Inc., Araldite® MY721) N, N-bis (oxylanylmethyl) -4- (oxylanylmethoxy) aniline (N, N, O- Triglycidyl-p-aminophenol, manufactured by Mitsubishi Chemical Corporation, jER® 630 and JER® 630LSD, or ADEKA EP-3950S and EP-3950SL, Huntsman Advanced Materials Araldite ( Registered trademarks) MY0500,), N, N, N', N'-tetraglycidyl-2,2'-diethyl-4,4'-methylenedianiline, N, N, N', N'-tetraglycidyl-m -Xylylene diamine,
Specific examples of the bifunctional glycidylamine type epoxy resin include N, N-diglycidylaniline, N, N-bis (oxylanylmethyl) -2- (methylaniline) (N, N-diglycidyl-o-toluidine, EP-3980S manufactured by ADEKA Corporation) can be mentioned.
In addition, a material obtained by modifying the epoxy resin with urethane can be used as the epoxy resin containing (A) nitrogen atom, and specific examples thereof include EPU-73B manufactured by ADEKA Corporation.
(A)窒素原子を含むエポキシ樹脂は、固形エポキシ樹脂、半固形エポキシ樹脂、液状エポキシ樹脂の何れであってもよいが、ドライフィルムや樹脂付き銅箔の製造の点で液状または半固形のエポキシ樹脂、特に液状または半固形のグリシジルアミン型のエポキシ樹脂を用いることが好ましい。 (A) The epoxy resin containing a nitrogen atom may be a solid epoxy resin, a semi-solid epoxy resin, or a liquid epoxy resin, but is a liquid or semi-solid epoxy in terms of producing a dry film or a copper foil with a resin. It is preferable to use a resin, particularly a liquid or semi-solid glycidylamine type epoxy resin.
本明細書において、固形エポキシ樹脂とは40℃で固体状であるエポキシ樹脂をいい、半固形エポキシ樹脂とは20℃で固体状であり、40℃で液状であるエポキシ樹脂をいい、液状エポキシ樹脂とは20℃で液状のエポキシ樹脂をいう。液状の判定は、危険物の試験及び性状に関する省令(平成元年自治省令第1号)の別紙第2の「液状の確認方法」に準じて行う。例えば、特開2016−079384の段落23〜25に記載の方法にて行なう。 In the present specification, the solid epoxy resin refers to an epoxy resin that is solid at 40 ° C., and the semi-solid epoxy resin refers to an epoxy resin that is solid at 20 ° C. and liquid at 40 ° C., and is a liquid epoxy resin. Refers to an epoxy resin that is liquid at 20 ° C. Judgment of liquidity is carried out in accordance with the "Liquid confirmation method" of Attachment 2 of the Ministerial Ordinance on Dangerous Goods Testing and Properties (Ministerial Ordinance No. 1 of 1989). For example, the method described in paragraphs 23 to 25 of JP-A-2016-079384 is used.
(A)窒素原子を含むエポキシ樹脂、特にグリシジルアミン型エポキシ樹脂を樹脂組成物の硬化成分として用いた場合、従来は、硬化物の架橋密度が高くなり、高い耐熱性は得られるものの、誘電特性が悪化すると考えられていた。
一方で、活性エステル基を有する化合物は、フェノール系硬化剤よりも導体に対する密着性が低いことが知られているため、上記比率のようにエポキシ基よりも活性エステル基の方が多い硬化性樹脂組成物においては、導体に対する密着性が悪くなると考えられていた。しかしながら、本発明の硬化性樹脂組成物では、(A)窒素原子を含むエポキシ樹脂を用いるにもかかわらず、(B)窒素原子を含まないエポキシ樹脂、(C)活性エステル基を有する化合物および(D)無機フィラーを併用し、かつ、(A)、(B)エポキシ樹脂と(C)活性エステル基を有する化合物との比を活性エステル基の方が多い特定範囲にしたことにより、高い耐熱性、低誘電正接、及び導体に対する高い密着性の全てを兼ね備えた硬化物が得られる。このような効果が得られた一因としては、(A)窒素原子を含むエポキシ樹脂を含有する樹脂組成物が適度な架橋密度で硬化したことによるものと考えられる。
(A) When an epoxy resin containing a nitrogen atom, particularly a glycidylamine type epoxy resin, is used as a curing component of the resin composition, conventionally, the crosslinked density of the cured product is high and high heat resistance can be obtained, but dielectric properties are obtained. Was thought to worsen.
On the other hand, since it is known that a compound having an active ester group has lower adhesion to a conductor than a phenolic curing agent, a curable resin having more active ester groups than an epoxy group as shown in the above ratio. In the composition, it was thought that the adhesion to the conductor was deteriorated. However, in the curable resin composition of the present invention, although (A) an epoxy resin containing a nitrogen atom is used, (B) an epoxy resin containing no nitrogen atom, (C) a compound having an active ester group, and ( High heat resistance is achieved by using D) an inorganic filler in combination and setting the ratio of the epoxy resins (A) and (B) to the compound having an active ester group to a specific range in which the number of active ester groups is larger. , A cured product having all of low dielectric normal contact and high adhesion to a conductor can be obtained. It is considered that one of the reasons why such an effect was obtained is that (A) the resin composition containing the epoxy resin containing a nitrogen atom was cured at an appropriate crosslink density.
[(B)窒素原子を含まないエポキシ樹脂]
本発明の硬化性樹脂組成物は、(A)窒素原子を含むエポキシ樹脂の他に、(B)窒素原子を含まないエポキシ樹脂を更に含む。(B)窒素原子を含まないエポキシ樹脂は、エポキシ基を有する樹脂であり、従来公知のものをいずれも使用することができ、好ましくは分子中にエポキシ基を2個有する2官能性エポキシ樹脂、分子中にエポキシ基を3個以上有する多官能エポキシ樹脂等が挙げられる。なお、水素添加されたエポキシ樹脂であってもよい。また、(B)窒素原子を含まないエポキシ樹脂は、固形エポキシ樹脂、半固形エポキシ樹脂、液状エポキシ樹脂の何れか1種または2種以上であってもよいが、固形エポキシ樹脂であることが好ましい。固形、半固形、液状エポキシ樹脂の定義、およびその判定方法は、(A)窒素原子を含むエポキシ樹脂について上述したとおりである。
[(B) Epoxy resin containing no nitrogen atom]
The curable resin composition of the present invention further contains (B) an epoxy resin containing no nitrogen atom in addition to (A) an epoxy resin containing a nitrogen atom. (B) The epoxy resin containing no nitrogen atom is a resin having an epoxy group, and any conventionally known epoxy resin can be used, preferably a bifunctional epoxy resin having two epoxy groups in the molecule. Examples thereof include a polyfunctional epoxy resin having three or more epoxy groups in the molecule. It may be a hydrogenated epoxy resin. Further, the epoxy resin (B) containing no nitrogen atom may be any one or more of a solid epoxy resin, a semi-solid epoxy resin, and a liquid epoxy resin, but is preferably a solid epoxy resin. .. The definitions of solid, semi-solid, and liquid epoxy resins, and the methods for determining them, are as described above for (A) epoxy resins containing nitrogen atoms.
(B)窒素原子を含まないエポキシ樹脂として使用される固形エポキシ樹脂としては、DIC社製EPICLON HP−4700(ナフタレン型エポキシ樹脂)、日本化薬社製NC−7000L(ナフタレン骨格含有多官能固形エポキシ樹脂)、新日鐵化学社製ESN−475V等のナフタレン型エポキシ樹脂;日本化薬社製EPPN−502H(トリスフェノールエポキシ樹脂)等のフェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物のエポキシ化物(トリスフェノール型エポキシ樹脂);DIC社製EPICLON HP−7200H(ジシクロペンタジエン骨格含有多官能固形エポキシ樹脂)等のジシクロペンタジエンアラルキル型エポキシ樹脂;日本化薬社製NC−3000H、NC−3000L(ビフェニル骨格含有多官能固形エポキシ樹脂)等のビフェニルアラルキル型エポキシ樹脂;DIC社製EPICLON N660、EPICLON N690、日本化薬社製EOCN−104S等のノボラック型エポキシ樹脂;三菱ケミカル社製YX−4000等のビフェニル型エポキシ樹脂;新日鉄住金化学社製TX0712等のリン含有エポキシ樹脂が挙げられる。固形エポキシ樹脂を含むことにより、硬化物のガラス転移温度が高くなり耐熱性に優れる。固形エポキシ樹脂の中でも、より高Tgかつ低誘電正接の硬化物が得られることから、ESN−475VやNC3000Hのように、芳香族化合物と、フェノールやナフトールがメチレン鎖で繋がった骨格を有するエポキシ樹脂が好ましい。 (B) Examples of the solid epoxy resin used as the epoxy resin containing no nitrogen atom include EPICLON HP-4700 (naphthalene type epoxy resin) manufactured by DIC and NC-7000L (polyfunctional solid epoxy containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd. Resin), naphthalene type epoxy resin such as ESN-475V manufactured by Nippon Steel Chemical Co., Ltd .; condensate of phenols such as EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. and aromatic aldehyde having phenolic hydroxyl group. (Trisphenol type epoxy resin); Dicyclopentadiene aralkyl type epoxy resin such as EPICLON HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by DIC; NC-3000H, NC manufactured by Nippon Kayaku Co., Ltd. Biphenyl aralkyl type epoxy resin such as -3000L (biphenyl skeleton-containing polyfunctional solid epoxy resin); Novorak type epoxy resin such as EPICLON N660 and EPICLON N690 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku Co., Ltd .; YX- Biphenyl type epoxy resin such as 4000; phosphorus-containing epoxy resin such as TX0712 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. can be mentioned. By containing the solid epoxy resin, the glass transition temperature of the cured product becomes high and the heat resistance is excellent. Among solid epoxy resins, a cured product having a higher Tg and a low dielectric loss tangent can be obtained. Therefore, an epoxy resin having a skeleton in which an aromatic compound and phenol or naphthol are linked by a methylene chain, such as ESN-475V and NC3000H, can be obtained. Is preferable.
半固形エポキシ樹脂としては、DIC社製EPICLON 860、EPICLON 900−IM、EPICLON EXA―4816、EPICLON EXA−4822、東都化成社製エポトートYD−134、三菱ケミカル社製jER834、jER872、住友化学社製ELA−134等のビスフェノールA型エポキシ樹脂;DIC社製EPICLON HP−4032等のナフタレン型エポキシ樹脂;DIC社製EPICLON N−740等のフェノールノボラック型エポキシ樹脂等が挙げられる。半固形状エポキシ樹脂を含むことにより、硬化物のガラス転移温度(Tg)が高く、線熱膨張係数(CTE)が低くなり、クラック耐性に優れる。また、半固形エポキシ樹脂を含むことにより、ドライフィルムの保存安定性に優れ、割れや剥がれを防止することができる。 As semi-solid epoxy resins, DIC's EPICLON 860, EPICLON 900-IM, EPICLON EXA-4816, EPICLON EXA-4822, Toto Kasei's Epototo YD-134, Mitsubishi Chemical's jER834, jER872, Sumitomo Chemical's ELA Examples thereof include bisphenol A type epoxy resin such as −134; naphthalene type epoxy resin such as EPICLON HP-4032 manufactured by DIC; and phenol novolac type epoxy resin such as EPICLON N-740 manufactured by DIC. By containing the semi-solid epoxy resin, the glass transition temperature (Tg) of the cured product is high, the coefficient of linear thermal expansion (CTE) is low, and the crack resistance is excellent. Further, by containing the semi-solid epoxy resin, the storage stability of the dry film is excellent, and cracking and peeling can be prevented.
液状エポキシ樹脂としては、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、ビスフェノールAF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、tert−ブチル−カテコール型エポキシ樹脂、脂環式エポキシ樹脂、窒素以外のヘテロ原子を含む複素環式エポキシ樹脂等が挙げられる。液状エポキシ樹脂を含むことにより、ドライフィルムのしなやかさを向上させることができる。
(B)窒素原子を含まないエポキシ樹脂として、また、固形エポキシ樹脂と液状エポキシ樹脂と半固形エポキシ樹脂とを併用してもよい。
Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, alicyclic epoxy resin, and heteroatoms other than nitrogen. Examples thereof include a heterocyclic epoxy resin containing. By containing the liquid epoxy resin, the suppleness of the dry film can be improved.
(B) As the epoxy resin containing no nitrogen atom, a solid epoxy resin, a liquid epoxy resin, and a semi-solid epoxy resin may be used in combination.
いずれの場合にも、(A)窒素原子を含むエポキシ樹脂と、(B)窒素原子を含まないエポキシ樹脂の合計質量における、液状エポキシ樹脂と半固形エポキシ樹脂の割合を5%〜50%の範囲にすることが好ましい。これによりドライフィルムの樹脂層のタックフリー性および柔軟性のバランスが良好となる。 In each case, the ratio of the liquid epoxy resin and the semi-solid epoxy resin to the total mass of the (A) nitrogen atom-containing epoxy resin and the (B) nitrogen atom-free epoxy resin is in the range of 5% to 50%. Is preferable. As a result, the balance between the tack-free property and the flexibility of the resin layer of the dry film is improved.
(A)窒素原子を含むエポキシ樹脂と、(B)窒素原子を含まないエポキシ樹脂は、それぞれ1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。(A)窒素原子を含むエポキシ樹脂と(B)窒素原子を含まないエポキシ樹脂の配合量は、硬化性樹脂組成物中の固形分を100質量%に対して、より低熱膨張係数かつ低吸湿性の硬化物が得られることから、40質量%以下であることが好ましく、35質量%以下であることがより好ましく、30質量%以下であることがさらにより好ましく、20質量%以下であることが特に好ましい。また、硬化性の観点から、下限が1質量%以上であることが好ましく、3質量%以上であることがより好ましい。
また、(A)窒素原子を含むエポキシ樹脂(A成分)と(B)窒素原子を含まないエポキシ樹脂(B成分)の合計質量におけてA成分が占める質量の割合は、0.1〜0.6((A)/(A)+(B))であることが好ましい。
The epoxy resin (A) containing a nitrogen atom and the epoxy resin (B) containing no nitrogen atom may be used alone or in combination of two or more. The blending amount of the epoxy resin containing (A) nitrogen atom and the epoxy resin containing no nitrogen atom (B) has a lower thermal expansion coefficient and lower hygroscopicity with respect to 100% by mass of the solid content in the curable resin composition. 40% by mass or less is preferable, 35% by mass or less is more preferable, 30% by mass or less is further more preferable, and 20% by mass or less is preferable. Especially preferable. Further, from the viewpoint of curability, the lower limit is preferably 1% by mass or more, and more preferably 3% by mass or more.
Further, the ratio of the mass occupied by the component A to the total mass of the epoxy resin (A component) containing the nitrogen atom (A component) and the epoxy resin (B component) not containing the nitrogen atom is 0.1 to 0. It is preferably .6 ((A) / (A) + (B)).
本発明の硬化性樹脂組成物は、本発明の効果を損なわない範囲で、(A)窒素原子を含むエポキシ樹脂および(B)窒素原子を含まないエポキシ樹脂以外の熱硬化性樹脂を含有してもよく、例えば、イソシアネート化合物、ブロックイソシアネート化合物、アミノ樹脂、ベンゾオキサジン樹脂、カルボジイミド樹脂、シクロカーボネート化合物、多官能オキセタン化合物、エピスルフィド樹脂、マレイミド樹脂などの公知慣用の熱硬化性樹脂を使用することができる。 The curable resin composition of the present invention contains (A) a thermosetting resin containing a nitrogen atom and (B) a thermosetting resin other than the epoxy resin containing no nitrogen atom, as long as the effect of the present invention is not impaired. It is also possible to use known and commonly used thermosetting resins such as isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional oxetane compounds, episulfide resins and maleimide resins. it can.
[(C)活性エステル基を有する化合物]
本発明の硬化性樹脂組成物は、A成分およびB成分の硬化剤として(C)活性エステル基を有する化合物を含む。
(C)活性エステル基を有する化合物は、一分子中に1個以上、好ましくは2個以上の活性エステル基.を有する化合物である。活性エステル基を有する化合物は、一般に、カルボン酸化合物とヒドロキシ化合物との縮合反応によって得ることができる。中でも、ヒドロキシ化合物としてフェノール化合物またはナフトール化合物を用いて得られる活性エステル基を有する化合物が好ましい。フェノール化合物またはナフトール化合物としては、ハイドロキノン、レゾルシン、ビスフェノールA、ビスフェノールF、ビスフェノールS、フェノールフタリン、メチル化ビスフェノールA、メチル化ビスフェノールF、メチル化ビスフェノールS、フェノール、o−クレゾール、m−クレゾール、p−クレゾール、カテコール、α−ナフトール、β−ナフトール、1,5−ジヒドロキシナフタレン、1,6−ジヒドロキシナフタレン、2,6−ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、フロログルシン、ベンゼントリオール、ジシクロペンタジエニルジフェノール、フェノールノボラック等が挙げられる。また、(C)活性エステル基を有する化合物としては、ナフタレンジオールアルキル/安息香酸型でもよい。(C)活性エステル基を有する化合物は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。(C)活性エステル基を有する化合物としては、ベンゼン、α−ナフトール、β−ナフトールおよびジシクロペンタジエン骨格のいずれかを有するものが好ましい。
[(C) Compound having active ester group]
The curable resin composition of the present invention contains (C) a compound having an active ester group as a curing agent for components A and B.
(C) The compound having an active ester group is a compound having one or more, preferably two or more active ester groups in one molecule. A compound having an active ester group can generally be obtained by a condensation reaction of a carboxylic acid compound and a hydroxy compound. Of these, a compound having an active ester group obtained by using a phenol compound or a naphthol compound as the hydroxy compound is preferable. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, benzenetriol , Dicyclopentadienyldiphenol, phenol novolac and the like. Further, as the compound (C) having an active ester group, a naphthalenediol alkyl / benzoic acid type may be used. (C) As the compound having an active ester group, one type may be used alone, or two or more types may be used in combination. (C) As the compound having an active ester group, a compound having any one of benzene, α-naphthol, β-naphthol and a dicyclopentadiene skeleton is preferable.
(C)活性エステル基を有する化合物の配合量は、樹脂組成物中の固形分を100質量%とした場合、硬化物の強度の観点から、上限が40質量%以下であることが好ましく、30質量%以下であることが特に好ましい。また、より低誘電正接の硬化物が得られることから、下限が3質量%以上であることが好ましく、5質量%以上であることがより好ましい。本発明の硬化性樹脂組成物においては、(A)窒素原子を含むエポキシ樹脂および(B)窒素原子を含まないエポキシ樹脂におけるエポキシ基の総量の、(C)活性エステル基を有する化合物におけるエステル基の総量に対する比が0.2〜0.6とされることから、これを考慮して、(C)活性エステル基を有する化合物の使用量を決定することは言うまでもない。 The upper limit of the compounding amount of the compound having the (C) active ester group is preferably 40% by mass or less from the viewpoint of the strength of the cured product, when the solid content in the resin composition is 100% by mass. It is particularly preferable that it is mass% or less. Further, since a cured product having a lower dielectric loss tangent can be obtained, the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. In the curable resin composition of the present invention, (A) the total amount of epoxy groups in the epoxy resin containing a nitrogen atom and (B) the epoxy resin containing no nitrogen atom, and (C) the ester group in the compound having an active ester group. Since the ratio of the compound to the total amount of the epoxy is 0.2 to 0.6, it goes without saying that the amount of the compound having the (C) active ester group to be used is determined in consideration of this.
(C)活性エステル基を有する化合物の中でも、下記(C1)および(C2)の活性エステル基を有する化合物を好適に用いることができる。 Among the compounds having the active ester groups (C), the compounds having the following active ester groups (C1) and (C2) can be preferably used.
(C1)
(C1)活性エステル基を有する化合物(活性エステル化合物ともいう)は、(c1)脂肪族環状炭化水素基を介してフェノール類が結節された分子構造を有するフェノール樹脂、(c2)芳香族ジカルボン酸またはそのハライド、および、(c3)芳香族モノヒドロキシ化合物を反応させて得られる構造を有するものである。前記(c2)芳香族ジカルボン酸またはそのハライド中のカルボキシル基または酸ハライド基1モルに対して、前記(c1)フェノール樹脂中のフェノール性水酸基が0.05〜0.75モル、前記(c3)芳香族モノヒドロキシ化合物が0.25〜0.95モルとなる割合で反応させて得られる構造を有するものが好ましい。
(C1)
The (C1) compound having an active ester group (also referred to as an active ester compound) is (c1) a phenol resin having a molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group, and (c2) an aromatic dicarboxylic acid. Alternatively, it has a structure obtained by reacting the halide and the (c3) aromatic monohydroxy compound. The phenolic hydroxyl group in the (c1) phenolic resin is 0.05 to 0.75 mol with respect to 1 mol of the carboxyl group or the acid halide group in the (c2) aromatic dicarboxylic acid or its halide, and the above (c3). Those having a structure obtained by reacting an aromatic monohydroxy compound at a ratio of 0.25 to 0.95 mol are preferable.
ここで(c1)フェノール樹脂において、脂肪族環状炭化水素基を介してフェノール類が結節された分子構造とは、1分子中に二重結合を2個含有する不飽和脂肪族環状炭化水素化合物とフェノール類とを重付加反応させて得られる構造が挙げられる。ここで、フェノール類としては、無置換フェノール、およびアルキル基、アルケニル基、アリル基、アリール基、アラルキル基或いはハロゲン基等が1個または複数個置換した置換フェノール類が挙げられる。置換フェノールの具体的としては、クレゾール、キシレノール、エチルフェノール、イソプロピルフェノール、ブチルフェノール、オクチルフェノール、ノニルフェノール、ビニルフェノール、イソプロペニルフェノール、アリルフェノール、フェニルフェノール、ベンジルフェノール、クロルフェノール、ブロムフェノール、ナフトール、ジヒドロキシナフタレン等が例示されるが、これらに限定されるものではない。またこれらの混合物を用いても構わない。これらの中でも流動性および硬化性が優れる点から無置換フェノールが特に好ましい。 Here, in the (c1) phenol resin, the molecular structure in which phenols are knotted via an aliphatic cyclic hydrocarbon group is an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule. Examples thereof include a structure obtained by a double addition reaction with phenols. Here, examples of the phenols include unsubstituted phenols and substituted phenols in which one or more alkyl groups, alkenyl groups, allyl groups, aryl groups, aralkyl groups, halogen groups and the like are substituted. Specific examples of the substituted phenol include cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorphenol, bromphenol, naphthol, and dihydroxynaphthalene. Etc., but are not limited to these. Moreover, you may use a mixture of these. Among these, unsubstituted phenol is particularly preferable from the viewpoint of excellent fluidity and curability.
また、不飽和脂環族環状炭化水素化合物としては、具体的には、ジシクロペンタジエン、テトラヒドロインデン、4−ビニルシクロヘキセン、5−ビニルノルボナ−2−エン、α−ピネン、β−ピネン、リモネン等が挙げられる。これらの中でも特性バランス、特に耐熱性、吸湿性の点からジシクロペンタジエンが好ましい。またジシクロペンタジエンは石油留分中に含まれることから、工業用ジシクロペンタジエンには他の脂肪族或いは芳香族性ジエン類等が不純物として含有されることがあるが、耐熱性、硬化性、成形性等を考慮すると、ジシクロペンタジエンの純度90質量%以上の製品であることが望ましい。 Specific examples of the unsaturated alicyclic hydrocarbon compound include dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorbona-2-ene, α-pinene, β-pinene, and limonene. Can be mentioned. Among these, dicyclopentadiene is preferable from the viewpoint of characteristic balance, particularly heat resistance and hygroscopicity. Since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain other aliphatic or aromatic diene as impurities, but it has heat resistance and curability. Considering moldability and the like, it is desirable that the product has a purity of 90% by mass or more of dicyclopentadiene.
次に、前記(c2)芳香族ジカルボン酸またはそのハライドは、イソフタル酸、テレフタル酸、1,4−、2,3−、あるいは2,6−ナフタレンジカルボン酸等の芳香族ジカルボン酸、およびこれらの酸フッ化物、酸塩化物、酸臭化物、酸ヨウ化物等の酸ハロゲン化物が挙げられる。これらのなかでも特に反応性が良好である点から芳香族ジカルボン酸の酸塩化物であること、なかでもイソフタル酸のジクロライド、テレフタル酸のジクロライドが好ましく、特にイソフタル酸のジクロライドが好ましい。 Next, the (c2) aromatic dicarboxylic acid or halide thereof is an aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, 1,4-, 2,3-, or 2,6-naphthalenedicarboxylic acid, and these. Examples thereof include acid halides such as acid fluorides, acid acid salts, acid bromides and acid iodides. Among these, an acid chloride of an aromatic dicarboxylic acid is preferable from the viewpoint of particularly good reactivity, and dichloride of isophthalic acid and dichloride of terephthalic acid are preferable, and dichloride of isophthalic acid is particularly preferable.
次に、(c3)芳香族モノヒドロキシ化合物としては、例えば、フェノール;o−クレゾール、m−クレゾール、p−クレゾール、3,5−キシレノール等のアルキルフェノール類;o−フェニルフェノール、p−フェニルフェノール、2−ベンジルフェノール、4−ベンジルフェノール、4−(α−クミル)フェノール等のアラルキルフェノール類;α−ナフトール、β−ナフトール等のナフトール類が挙げられる。これらのなかでも、特に硬化物の誘電正接が低くなる点からα−ナフトール、β−ナフトールが好ましい。 Next, as the (c3) aromatic monohydroxy compound, for example, phenol; alkylphenols such as o-cresol, m-cresol, p-cresol, 3,5-xylenol; o-phenylphenol, p-phenylphenol, Aralkylphenols such as 2-benzylphenol, 4-benzylphenol and 4- (α-cumyl) phenol; naphthols such as α-naphthol and β-naphthol can be mentioned. Among these, α-naphthol and β-naphthol are particularly preferable from the viewpoint of lowering the dielectric loss tangent of the cured product.
(C1)活性エステル化合物は、(c1)フェノール樹脂、(c2)芳香族ジカルボン酸またはそのハライド、および、(c3)芳香族モノヒドロキシ化合物を反応させて得られる構造を有するものであるが、特に、下記一般式(1)
で表される構造のものがとりわけ硬化物の誘電正接が低く、かつ、有機溶剤に溶解させた際の溶液粘度が低くなる点から好ましい。前記ベンゼン環またはナフタレン環を有する基は、特に限定されず、フェニル基、ナフチル基等でもよく、また、他の原子を介してベンゼン環またはナフタレン環が分子末端に結合していてもよく、置換基を有していてもよい。また、(C1)活性エステル化合物は、その分子末端にナフタレン環を有するものであることが好ましい。
The (C1) active ester compound has a structure obtained by reacting (c1) a phenol resin, (c2) an aromatic dicarboxylic acid or a halide thereof, and (c3) an aromatic monohydroxy compound, and in particular. , The following general formula (1)
The structure represented by is particularly preferable because the dielectric loss tangent of the cured product is low and the solution viscosity when dissolved in an organic solvent is low. The group having a benzene ring or a naphthalene ring is not particularly limited, and may be a phenyl group, a naphthyl group, or the like, or a benzene ring or a naphthalene ring may be bonded to the molecular terminal via another atom, and is substituted. It may have a group. Further, the (C1) active ester compound preferably has a naphthalene ring at the molecular terminal thereof.
特に、上記一般式(1)においてnの値、即ち、繰り返し単位の平均値が0.25〜1.5の範囲にあるものが、溶液粘度が低くビルドアップ用ドライフィルムへの製造が容易となる点から好ましい。また、上記一般式(1)中、kの値は0であることが、高耐熱性と低誘電正接の観点から好ましい。 In particular, in the above general formula (1), the value of n, that is, the average value of the repeating units in the range of 0.25 to 1.5 has a low solution viscosity and is easy to produce into a dry film for build-up. It is preferable from the point of view. Further, in the above general formula (1), it is preferable that the value of k is 0 from the viewpoint of high heat resistance and low dielectric loss tangent.
ここで上記一般式(1)中のnは以下の様にして求めることができる。
[一般式(1)中のnの求め方]
下記の条件にて行ったGPC測定によりn=1、n=2、n=3、n=4のそれぞれに対応するスチレン換算分子量(α1、α2、α3、α4)と、n=1、n=2、n=3、n=4のそれぞれの理論分子量(β1、β2、β3、β4)との比率(β1/α1、β2/α2、β3/α3、β4/α4)を求め、これら(β1/α1〜β4/α4)の平均値を求める。GPCで求めた数平均分子量(Mn)にこの平均値を掛け合わせた数値を平均分子量とする。次いで、前記一般式(1)の分子量を前記平均分子量としてnの値を算出する。
Here, n in the above general formula (1) can be obtained as follows.
[How to find n in general formula (1)]
The styrene-equivalent molecular weights (α1, α2, α3, α4) corresponding to each of n = 1, n = 2, n = 3, and n = 4 and n = 1, n = by GPC measurement performed under the following conditions. The ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) to the theoretical molecular weights (β1, β2, β3, β4) of 2, n = 3, and n = 4 were obtained, and these (β1 / Obtain the average value of α1 to β4 / α4). The value obtained by multiplying the number average molecular weight (Mn) obtained by GPC by this average value is defined as the average molecular weight. Next, the value of n is calculated by using the molecular weight of the general formula (1) as the average molecular weight.
(GPC測定条件)
測定装置:東ソー社製「HLC−8220 GPC」、
カラム:東ソー社製ガードカラム「HXL−L」
+東ソー社製「TSK−GEL G2000HXL」
+東ソー社製「TSK−GEL G2000HXL」
+東ソー社製「TSK−GEL G3000HXL」
+東ソー社製「TSK−GEL G4000HXL」
検出器:RI(示差屈折径)
データ処理:東ソー社製「GPC−8020モデルIIバージョン4.10」
測定条件:カラム温度 40℃
展開溶媒 テトラヒドロフラン
流速 1.0ml/分
標準:前記「GPC−8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
(使用ポリスチレン)
東ソー社製「A−500」
東ソー社製「A−1000」
東ソー社製「A−2500」
東ソー社製「A−5000」
東ソー社製「F−1」
東ソー社製「F−2」
東ソー社製「F−4」
東ソー社製「F−10」
東ソー社製「F−20」
東ソー社製「F−40」
東ソー社製「F−80」
東ソー社製「F−128」
試料:樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)。
(GPC measurement conditions)
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd.,
Column: Tosoh guard column "H XL- L"
+ "TSK-GEL G2000HXL" manufactured by Tosoh
+ "TSK-GEL G2000HXL" manufactured by Tosoh
+ "TSK-GEL G3000HXL" manufactured by Tosoh
+ "TSK-GEL G4000HXL" manufactured by Tosoh
Detector: RI (differential refractometer)
Data processing: Tosoh "GPC-8020 Model II Version 4.10"
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Version 4.10".
(Polystyrene used)
"A-500" manufactured by Tosoh
"A-1000" manufactured by Tosoh
Tosoh "A-2500"
"A-5000" manufactured by Tosoh
Tosoh "F-1"
Tosoh "F-2"
Tosoh "F-4"
"F-10" manufactured by Tosoh
Tosoh "F-20"
Tosoh "F-40"
Tosoh "F-80"
"F-128" manufactured by Tosoh
Sample: A solution obtained by filtering 1.0 mass% of a tetrahydrofuran solution in terms of resin solid content with a microfilter (50 μl).
(c1)フェノール樹脂、(c2)芳香族ジカルボン酸またはそのハライド、および、(c3)芳香族モノヒドロキシ化合物を反応させる方法は、具体的には、これらの各成分をアルカリ触媒の存在下に反応させることができる。
ここで使用し得るアルカリ触媒としては、水酸化ナトリウム、水酸化カリウム、トリエチルアミン、ピリジン等が挙げられる。これらのなかでも特に水酸化ナトリウム、水酸化カリウムが水溶液の状態で使用することができ、生産性が良好となる点から好ましい。
The method of reacting (c1) a phenol resin, (c2) an aromatic dicarboxylic acid or a halide thereof, and (c3) an aromatic monohydroxy compound specifically reacts each of these components in the presence of an alkaline catalyst. Can be made to.
Examples of the alkaline catalyst that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. Among these, sodium hydroxide and potassium hydroxide are particularly preferable because they can be used in an aqueous solution state and the productivity is improved.
前記反応は、具体的には有機溶媒の存在下、(c1)フェノール樹脂、(c2)芳香族ジカルボン酸またはそのハライド、および、(c3)芳香族モノヒドロキシ化合物を混合し、前記アルカリ触媒またはその水溶液を連続的乃至断続的に滴下しながら反応させる方法が挙げられる。その際、アルカリ触媒の水溶液の濃度は、3.0〜30%の範囲であることが好ましい。また、ここで使用し得る有機溶媒としては、トルエン、ジクロロメタンなどが挙げられる。 Specifically, in the reaction, (c1) a phenol resin, (c2) an aromatic dicarboxylic acid or a halide thereof, and (c3) an aromatic monohydroxy compound are mixed in the presence of an organic solvent, and the alkaline catalyst or the same thereof. Examples thereof include a method in which the aqueous solution is continuously or intermittently dropped and reacted. At that time, the concentration of the aqueous solution of the alkaline catalyst is preferably in the range of 3.0 to 30%. Further, examples of the organic solvent that can be used here include toluene and dichloromethane.
反応終了後は、アルカリ触媒の水溶液を用いている場合には、反応液を静置分液し、水層を取り除き、残った有機層を洗浄後の水層がほぼ中性になるまで繰り返し、目的とする樹脂を得ることができる。 After completion of the reaction, if an aqueous solution of an alkaline catalyst is used, the reaction solution is statically separated, the aqueous layer is removed, and the remaining organic layer is repeated until the washed aqueous layer becomes almost neutral. The target resin can be obtained.
このようにして得られる(C1)活性エステル基を有する化合物は、通常、有機溶媒溶液として得られる為、積層板用ワニスやビルドアップ用ドライフィルムとして用いる場合には、そのままで他の配合成分と混合し、更に、適宜、有機溶媒量を調節して目的とする熱硬化性樹脂組成物を製造することができる。なお、(C1)活性エステル化合物は、有機溶媒に溶解させて樹脂溶液とした際の溶融粘度が低いことを特徴としており、具体的には、固形分65%のトルエン溶液の活性エステル基を有する化合物にした場合の溶液粘度が300〜10,000mPa・s(25℃)となる。 Since the compound having the (C1) active ester group thus obtained is usually obtained as an organic solvent solution, when it is used as a varnish for a laminated board or a dry film for build-up, it can be used as it is with other compounding components. The desired thermosetting resin composition can be produced by mixing and further adjusting the amount of the organic solvent as appropriate. The (C1) active ester compound is characterized by having a low melt viscosity when dissolved in an organic solvent to prepare a resin solution, and specifically, it has an active ester group of a toluene solution having a solid content of 65%. When made into a compound, the solution viscosity is 300 to 10,000 mPa · s (25 ° C.).
(C2)
(C2)の活性エステル基を有する化合物は、下記一般式(2):
The compound having the active ester group of (C2) has the following general formula (2):
(式(2)中、X2はそれぞれ独立的に下記式(3):
(C2)の活性エステル基を有する化合物は、前記一般式(2)中の
式(2)中、mとnの関係を明確にするために、以下、いくつかのパターンを例示するが(C2)の活性エステル基を有する化合物はこれらに限定されるものではない。
たとえば、m=1のとき、式(2)は下記式(2−I)の構造を表す。
In the formula (2), in order to clarify the relationship between m and n, some patterns are exemplified below, but the compound having the active ester group of (C2) is not limited to these.
For example, when m = 1, the formula (2) represents the structure of the following formula (2-I).
式(2−I)中、nは1〜5の整数であり、nが2以上の場合にはqはそれぞれ独立的に0〜6の整数である。 In formula (2-I), n is an integer of 1 to 5, and when n is 2 or more, q is an integer of 0 to 6 independently.
また、たとえば、m=2のとき、式(2)は下記式(2−II)の構造を表す。 Further, for example, when m = 2, the formula (2) represents the structure of the following formula (2-II).
式(2−II)中、nはそれぞれ独立的に1〜5の整数であり、nが2以上の場合には、qはそれぞれ独立的に0〜6の整数である。 In formula (2-II), n is an integer of 1 to 5 independently, and when n is 2 or more, q is an integer of 0 to 6 independently.
(C2)の活性エステル基を有する化合物は、分子主骨格にナフチレンエーテル構造部位を有することから、より優れた耐熱性および難燃性を硬化物に付与できると共に、該構造部位が下記式(5)で表される構造部位で結合した構造を有することから、硬化物により優れた誘電特性を兼備させることができる。また、(C2)の活性エステル基を有する化合物の構造中、両末端の構造としてアリールオキシ基を有するものとしたことで、多層プリント基板用途においても十分高度な硬化物の耐熱分解性の向上が得られる。 Since the compound having the active ester group of (C2) has a naphthylene ether structural moiety in the molecular main skeleton, more excellent heat resistance and flame retardancy can be imparted to the cured product, and the structural moiety has the following formula (C2). Since it has a structure bonded at the structural portion represented by 5), the cured product can have more excellent dielectric properties. Further, in the structure of the compound having an active ester group of (C2), by adopting an aryloxy group as a structure at both ends, a sufficiently high degree of improvement in heat resistance of the cured product can be improved even in a multilayer printed circuit board application. can get.
(C2)の活性エステル基を有する化合物は、特に、硬化物の耐熱性に優れる点から、その軟化点が100〜200℃の範囲、特に100〜190℃の範囲にあるものが好ましい。 The compound having the active ester group of (C2) is preferably a compound having a softening point in the range of 100 to 200 ° C., particularly preferably in the range of 100 to 190 ° C., from the viewpoint of excellent heat resistance of the cured product.
(C2)の活性エステル基を有する化合物において、式(2)中のmは1〜6の整数であるものが挙げられる。なかでも、mが1〜5の整数であるものが好ましい。また、式(2)中のnはそれぞれ独立的に1〜5の整数であるものが挙げられる。なかでも、nが1〜3の整数であるものが好ましい。
式(2)中、mとnの関係を念のため記載するに、例えば、mが2以上の整数である場合、2以上のnが生じるが、その際、nはそれぞれ独立的な値である。すなわち、前記nの数値範囲内であるかぎり、同じ値であってもよいし、異なる値であってもよい。
Among the compounds having an active ester group of (C2), m in the formula (2) may be an integer of 1 to 6. Among them, those in which m is an integer of 1 to 5 are preferable. Further, n in the equation (2) may be an integer of 1 to 5 independently. Of these, those in which n is an integer of 1 to 3 are preferable.
In the formula (2), the relationship between m and n is described just in case. For example, when m is an integer of 2 or more, n of 2 or more occurs, but in that case, n is an independent value. is there. That is, as long as it is within the numerical range of n, it may be the same value or it may be a different value.
(C2)の活性エステル基を有する化合物において、式(2)中、qが1以上の場合、X2はナフタレン環構造中のいずれの位置に置換していてもよい。 In the compound having the active ester group of (C2), when q is 1 or more in the formula (2), X 2 may be substituted at any position in the naphthalene ring structure.
前記構造の両末端のアリールオキシ基は、フェノール、クレゾール、p−t−ブチルフェノール(パラ−ターシャリーブチルフェノール)、1−ナフトール、2−ナフトールなどの一価フェノール系化合物由来のものが挙げられる。なかでも、硬化物の耐熱分解性の観点から、フェノキシ基、トリルオキシ基または1−ナフチルオキシ基が好ましく、1−ナフチルオキシ基がさらに好ましい。 Examples of the aryloxy groups at both ends of the structure are those derived from monohydric phenolic compounds such as phenol, cresol, pt-butylphenol (paratershary butylphenol), 1-naphthol, and 2-naphthol. Among them, a phenoxy group, a triloxy group or a 1-naphthyloxy group is preferable, and a 1-naphthyloxy group is more preferable, from the viewpoint of thermostable decomposition of the cured product.
以下、(C2)の活性エステル基を有する化合物の製造方法について詳述する。
(C2)の活性エステル基を有する化合物の製造方法は、ジヒドロキシナフタレン化合物とベンジルアルコールとを、酸触媒の存在下に反応させてベンジル変性ナフタレン化合物を得る工程(以下、この工程を「工程1」と略記する場合がある)、次いで、得られたベンジル変性ナフタレン化合物と芳香族ジカルボン酸塩化物と一価フェノール系化合物とを反応させる工程(以下、この工程を「工程2」と略記する場合がある)とから構成される。
Hereinafter, the method for producing the compound having the active ester group of (C2) will be described in detail.
The method for producing the compound having an active ester group of (C2) is a step of reacting a dihydroxynaphthalene compound and a benzyl alcohol in the presence of an acid catalyst to obtain a benzyl-modified naphthalene compound (hereinafter, this step is referred to as "step 1"). (May be abbreviated as), then a step of reacting the obtained benzyl-modified naphthalene compound with an aromatic dicarboxylate compound and a monovalent phenolic compound (hereinafter, this step may be abbreviated as "step 2"). There is) and.
即ち、まず工程1において前記ジヒドロキシナフタレン化合物と、ベンジルアルコールとを酸触媒の存在下に反応させることにより、ナフチレン構造を主骨格としてその両末端にフェノール性水酸基を有し、かつ、該ナフチレン構造の芳香核上にベンジル基がペンダント状に結合した構造のベンジル変性ナフタレン化合物を得ることができる。ここで、特筆すべきは、一般に、ジヒドロキシナフタレン化合物を酸触媒下にナフチレンエーテル化した場合、分子量の調節は極めて困難で、高分子量のものとなるのに対し、上記製造方法は、ベンジルアルコールを併用することによって、このような高分子量化を抑制でき、電子材料用途に好適な樹脂を得ることができる。 That is, first, in step 1, the dihydroxynaphthalene compound and benzyl alcohol are reacted in the presence of an acid catalyst to have a naphthylene structure as a main skeleton and having phenolic hydroxyl groups at both ends thereof, and to have the naphthylene structure. A benzyl-modified naphthalene compound having a structure in which a benzyl group is bonded in a pendant shape on an aromatic nucleus can be obtained. Here, it should be noted that, in general, when a dihydroxynaphthalene compound is naphthylene etherified under an acid catalyst, it is extremely difficult to adjust the molecular weight and the molecular weight becomes high, whereas the above production method is benzyl alcohol. By using the above in combination, such a high molecular weight increase can be suppressed, and a resin suitable for use in electronic materials can be obtained.
更に、ベンジルアルコールの使用量を調節することによって、目的とする前記ベンジル変性ナフタレン化合物中のベンジル基の含有率を調節できることに加え、前記ベンジル変性ナフタレン化合物の溶融粘度自体も調節することが可能となる。即ち、通常、前記ジヒドロキシナフタレン化合物と、ベンジルアルコールとの反応割合は、モル基準で前記ジヒドロキシナフタレン化合物とベンジルアルコールとの反応比率(ジヒドロキシナフタレン化合物)/(ベンジルアルコール)が1/0.1〜1/10となる範囲から選択することができるが、耐熱性、難燃性、誘電特性、耐熱分解性とのバランスから、モル基準で前記ジヒドロキシナフタレン化合物とベンジルアルコールとの反応比率(ジヒドロキシナフタレン化合物)/(ベンジルアルコール)は1/0.5〜1/4.0となる範囲であることが好ましい。 Further, by adjusting the amount of benzyl alcohol used, in addition to being able to adjust the content of the benzyl group in the target benzyl-modified naphthalene compound, the melt viscosity itself of the benzyl-modified naphthalene compound can also be adjusted. Become. That is, usually, the reaction ratio of the dihydroxynaphthalene compound to benzyl alcohol is 1 / 0.1 to 1 for the reaction ratio of the dihydroxynaphthalene compound to benzyl alcohol (dihydroxynaphthalene compound) / (benzyl alcohol) on a molar basis. It can be selected from the range of 1/10, but the reaction ratio of the dihydroxynaphthalene compound to benzyl alcohol (dihydroxynaphthalene compound) is based on a molar balance from the balance between heat resistance, flame retardancy, dielectric properties, and heat decomposition resistance. / (Benzyl alcohol) is preferably in the range of 1 / 0.5 to 1 / 4.0.
ここで使用し得るジヒドロキシナフタレン化合物は、例えば、1,2−ジヒドロキシナフタレン、1,3−ジヒドロキシナフタレン、1,4−ジヒドロキシナフタレン、1,5−ジヒドロキシナフタレン、1,6−ジヒドロキシナフタレン、1,7−ジヒドロキシナフタレン、1,8−ジヒドロキシナフタレン、2,3−ジヒドロキシナフタレン、2,6−ジヒドロキシナフタレン、2,7−ジヒドロキシナフタレンなどが挙げられる。これらの中でも、得られるベンジル変性ナフタレン化合物の硬化物の難燃性が一層良好なものとなり、また、該硬化物の誘電正接も低くなり誘電特性が良好になる点から、1,6−ジヒドロキシナフタレンまたは2,7−ジヒドロキシナフタレンが好ましく、2,7−ジヒドロキシナフタレンがより好ましい。 The dihydroxynaphthalene compounds that can be used here are, for example, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7. Examples thereof include −dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene. Among these, 1,6-dihydroxynaphthalene is obtained because the cured product of the obtained benzyl-modified naphthalene compound has better flame retardancy, and the dielectric loss tangent of the cured product is lowered and the dielectric properties are improved. Alternatively, 2,7-dihydroxynaphthalene is preferable, and 2,7-dihydroxynaphthalene is more preferable.
前記工程1におけるジヒドロキシナフタレン化合物とベンジルアルコールとの反応において使用し得る酸触媒は、例えばリン酸、硫酸、塩酸などの無機酸、シュウ酸、ベンゼンスルホン酸、トルエンスルホン酸、メタンスルホン酸、フルオロメタンスルホン酸などの有機酸、塩化アルミニウム、塩化亜鉛、塩化第2錫、塩化第2鉄、ジエチル硫酸などのフリーデルクラフツ触媒が挙げられる。 The acid catalyst that can be used in the reaction between the dihydroxynaphthalene compound and benzyl alcohol in step 1 is, for example, inorganic acids such as phosphoric acid, sulfuric acid and hydrochloric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethane. Examples thereof include organic acids such as sulfonic acid, Friedel-Crafts catalysts such as aluminum chloride, zinc chloride, ferric chloride, ferric chloride and diethylsulfate.
また、上記した酸触媒の使用量は、目標とする変性率などにより適宜選択することができるが、例えば無機酸や有機酸の場合はジヒドロキシナフタレン化合物100質量部に対し、0.001〜5.0質量部、好ましくは0.01〜3.0質量部なる範囲であり、フリーデルクラフツ触媒の場合はジヒドロキシナフタレン化合物1モルに対し、0.2〜3.0モル、好ましくは0.5〜2.0モルとなる範囲であることが好ましい。 The amount of the acid catalyst used can be appropriately selected depending on the target modification rate and the like. For example, in the case of an inorganic acid or an organic acid, 0.001 to 5. The range is 0 parts by mass, preferably 0.01 to 3.0 parts by mass, and in the case of a Friedel-Crafts catalyst, 0.2 to 3.0 mol, preferably 0.5 to 3.0 mol, per 1 mol of the dihydroxynaphthalene compound. The range is preferably 2.0 mol.
前記工程1におけるジヒドロキシナフタレン化合物とベンジルアルコールとの反応は、無溶媒下で行うこともでき、反応系内の均一性を高める点から溶媒下で行うこともできる。かかる溶媒としては、例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジプロピルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテルなどのエチレングリコールやジエチレングリコールのモノまたはジエーテル;ベンゼン、トルエン、キシレンなどの非極性芳香族溶媒;ジメチルホルムアミドやジメチルスルホキシドなどの非プロトン性極性溶媒;クロロベンゼンなどが挙げられる。 The reaction between the dihydroxynaphthalene compound and benzyl alcohol in the step 1 can be carried out without a solvent, or can be carried out under a solvent from the viewpoint of enhancing the uniformity in the reaction system. Examples of such a solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether. Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether and other ethylene glycol and diethylene glycol mono or diether; non-polar aromatic solvents such as benzene, toluene and xylene; non-polar aromatic solvents such as dimethylformamide and dimethylsulfoxide. Protonic polar solvent; chlorobenzene and the like can be mentioned.
前記工程1の反応を行う具体的方法は、無溶媒下で、或いは前記溶媒存在下でジヒドロキシナフタレン化合物、ベンジルアルコールおよび前記酸触媒を溶解させ、60〜180℃、好ましくは80〜160℃程度の温度条件下に行うことができる。また、反応時間は特に限定されるものではないが、1〜10時間であることが好ましい。よって、当該反応は、具体的には、前記温度を1〜10時間保持することによって行うことができる。また、反応中に生成する水を系外に分留管などを用いて留去することが、反応が速やかに進行して生産性が向上する点から好ましい。 The specific method for carrying out the reaction in step 1 is to dissolve the dihydroxynaphthalene compound, benzyl alcohol and the acid catalyst in the absence of a solvent or in the presence of the solvent, and the temperature is about 60 to 180 ° C., preferably about 80 to 160 ° C. It can be done under temperature conditions. The reaction time is not particularly limited, but is preferably 1 to 10 hours. Therefore, the reaction can be carried out specifically by holding the temperature for 1 to 10 hours. Further, it is preferable to distill off the water generated during the reaction to the outside of the system using a fractional tube or the like because the reaction proceeds rapidly and the productivity is improved.
また、得られるベンジル変性ナフタレン化合物の着色が大きい場合は、それを抑制するために、反応系に酸化防止剤や還元剤を添加しても良い。酸化防止剤としては、例えば2,6−ジアルキルフェノール誘導体などのヒンダードフェノール系化合物、2価のイオウ系化合物、3価のリン原子を含む亜リン酸エステル系化合物などが挙られる。還元剤としては、例えば次亜リン酸、亜リン酸、チオ硫酸、亜硫酸、ハイドロサルファイトまたはこれらの塩などが挙げられる。 Further, when the obtained benzyl-modified naphthalene compound is heavily colored, an antioxidant or a reducing agent may be added to the reaction system in order to suppress it. Examples of the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing a trivalent phosphorus atom. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfite, hydrosulfite or salts thereof.
反応終了後は、酸触媒を中和処理、水洗処理あるいは分解することにより除去し、抽出、蒸留などの一般的な操作により、目的とするフェノール性水酸基を有する樹脂を分離することができる。中和処理や水洗処理は常法に従って行えばよく、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、アンモニア、トリエチレンテトラミン、アニリンなどの塩基性物質を中和剤として用いることができる。 After completion of the reaction, the acid catalyst can be removed by neutralization treatment, washing treatment or decomposition, and the resin having the desired phenolic hydroxyl group can be separated by general operations such as extraction and distillation. The neutralization treatment and the washing treatment may be carried out according to a conventional method. For example, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine and aniline can be used as the neutralizing agent.
ここで、前記芳香族ジカルボン酸塩化物としては、具体的には、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の酸塩化物などが挙げられる。なかでも、溶剤溶解性と耐熱性のバランスの点からイソフタル酸クロリド、テレフタル酸クロリドが好ましい。 Here, specific examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Examples include the acidified product of. Of these, isophthalic acid chloride and terephthalic acid chloride are preferable from the viewpoint of the balance between solvent solubility and heat resistance.
前記一価フェノール系化合物としては、具体的には、フェノール、クレゾール、p−t−ブチルフェノール、1−ナフトール、2−ナフトールなどが挙げられる。なかでも、フェノール、クレゾール、1−ナフトールが、カルボン酸クロリドとの反応性が良好である点から好ましく、耐熱分解性が良好である点から1−ナフトールがさらに好ましい。 Specific examples of the monovalent phenolic compound include phenol, cresol, pt-butylphenol, 1-naphthol, 2-naphthol and the like. Of these, phenol, cresol, and 1-naphthol are preferable from the viewpoint of good reactivity with carboxylic acid chloride, and 1-naphthol is more preferable from the viewpoint of good thermal decomposition resistance.
ここで、前記ベンジル変性ナフタレン化合物、芳香族ジカルボン酸塩化物、更に一価フェノール系化合物を反応させる方法は、具体的には、これらの各成分をアルカリ触媒の存在下に反応させることができる。 Here, in the method of reacting the benzyl-modified naphthalene compound, the aromatic dicarboxylic acid compound, and the monohydric phenol-based compound, specifically, each of these components can be reacted in the presence of an alkali catalyst.
ここで使用し得るアルカリ触媒としては、水酸化ナトリウム、水酸化カリウム、トリエチルアミン、ピリジン等が挙げられる。これらのなかでも特に水酸化ナトリウム、水酸化カリウムが水溶液の状態で使用することができ、生産性が良好となる点から好ましい。 Examples of the alkaline catalyst that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. Among these, sodium hydroxide and potassium hydroxide are particularly preferable because they can be used in an aqueous solution state and the productivity is improved.
前記反応は、具体的には有機溶媒の存在下、前記した各成分を混合し、前記アルカリ触媒またはその水溶液を連続的または断続的に滴下しながら反応させることができる。その際、アルカリ触媒の水溶液の濃度は、3.0〜30質量%の範囲であることが好ましい。また、ここで使用し得る有機溶媒としては、トルエン、ジクロロメタン、クロロホルムなどが挙げられる。 Specifically, the reaction can be carried out by mixing the above-mentioned components in the presence of an organic solvent and continuously or intermittently dropping the alkaline catalyst or an aqueous solution thereof. At that time, the concentration of the aqueous solution of the alkaline catalyst is preferably in the range of 3.0 to 30% by mass. Examples of the organic solvent that can be used here include toluene, dichloromethane, chloroform and the like.
反応終了後は、アルカリ触媒の水溶液を用いている場合には、反応液を静置分液し、水層を取り除き、残った有機層を洗浄後の水層がほぼ中性になるまで繰り返し、目的とする樹脂を得ることができる。 After completion of the reaction, if an aqueous solution of an alkaline catalyst is used, the reaction solution is statically separated, the aqueous layer is removed, and the remaining organic layer is repeated until the washed aqueous layer becomes almost neutral. The target resin can be obtained.
このようにして得られる(C2)の活性エステル基を有する化合物は、その軟化点が100〜200℃であると、有機溶剤への溶解性が高くなるため好ましい。 The compound having the active ester group (C2) thus obtained is preferable when the softening point is 100 to 200 ° C. because the solubility in an organic solvent is high.
本発明の熱硬化性樹脂組成物は、本発明の効果を損なわない範囲で、(C)活性エステル基を有する化合物以外の硬化剤を含有してもよく、例えば、フェノール性水酸基を有する化合物、ポリカルボン酸およびその酸無水物、シアネートエステル基を有する化合物、マレイミド基を有する化合物、脂環式オレフィン重合体等が挙げられる。 The thermosetting resin composition of the present invention may contain a curing agent other than the compound having the active ester group (C) as long as the effect of the present invention is not impaired. For example, a compound having a phenolic hydroxyl group. Examples thereof include polycarboxylic acids and their acid anhydrides, compounds having a cyanate ester group, compounds having a maleimide group, and alicyclic olefin polymers.
[(D)無機フィラー]
本発明の硬化性樹脂組成物は、(D)無機フィラーを含む。(D)無機フィラーを含むことによって、得られる硬化物の硬化収縮を抑制し、より低CTEとなり、密着性、硬度、絶縁層の周囲にある銅等の導体層と熱強度を合わせることによるクラック耐性等の熱特性を向上させることができる。(D)無機フィラーとしては従来公知の無機フィラーが使用でき、特定のものに限定されないが、例えば、硫酸バリウム、チタン酸バリウム、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカなどのシリカ、タルク、クレー、ノイブルグ珪土粒子、ベーマイト、炭酸マグネシウム、炭酸カルシウム、酸化チタン、酸化アルミニウム、水酸化アルミニウム、窒化ケイ素、窒化アルミニウム、ジルコン酸カルシウム等の体質顔料や、銅、錫、亜鉛、ニッケル、銀、パラジウム、アルミニウム、鉄、コバルト、金、白金等の金属粉体が挙げられる。(D)無機フィラーは球状粒子であることが好ましい。中でもシリカが好ましく、硬化性樹脂組成物の硬化物の硬化収縮を抑制し、より低CTEとなり、また、密着性、硬度などの特性を向上させることができる。(D)無機フィラーの平均粒子径(メディアン径、D50)は、0.01〜10μmであることが好ましい。(D)無機フィラーとしては、平均粒子径が0.01〜3μmのシリカであることが好ましい。なお、本明細書において、(D)無機フィラーの平均粒子径は、一次粒子の粒径だけでなく、二次粒子(凝集体)の粒径も含めた平均粒子径である。平均粒子径は、レーザー回折式粒子径分布測定装置により求めることができる。レーザー回折法による測定装置としては、マイクロトラック・ベル社製マイクロトラックMT3000IIなどが挙げられる。
[(D) Inorganic filler]
The curable resin composition of the present invention contains (D) an inorganic filler. (D) By containing the inorganic filler, the curing shrinkage of the obtained cured product is suppressed, the CTE becomes lower, and the adhesion, hardness, and cracks due to matching the thermal strength with the conductor layer such as copper around the insulating layer. Thermal properties such as resistance can be improved. As the inorganic filler (D), conventionally known inorganic fillers can be used and are not limited to specific ones, but for example, silica such as barium sulfate, barium titanate, amorphous silica, crystalline silica, molten silica, and spherical silica, etc. Tarku, clay, Neuburg siliceous earth particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, calcium zirconate and other extender pigments, copper, tin, zinc, nickel, Examples thereof include metal powders such as silver, palladium, aluminum, iron, cobalt, gold and platinum. The inorganic filler (D) is preferably spherical particles. Among them, silica is preferable, and the curing shrinkage of the cured product of the curable resin composition can be suppressed, the CTE can be lowered, and the properties such as adhesion and hardness can be improved. The average particle size (median diameter, D50) of the inorganic filler (D) is preferably 0.01 to 10 μm. The inorganic filler (D) is preferably silica having an average particle size of 0.01 to 3 μm. In the present specification, the average particle size of the (D) inorganic filler is an average particle size including not only the particle size of the primary particles but also the particle size of the secondary particles (aggregates). The average particle size can be determined by a laser diffraction type particle size distribution measuring device. Examples of the measuring device by the laser diffraction method include Microtrack MT3000II manufactured by Microtrack Bell.
(D)無機フィラーは、表面処理された無機フィラーであることが好ましい。表面処理としては、カップリング剤による表面処理や、アルミナ処理等の有機基を導入しない表面処理がされていてもよい。(D)無機フィラーの表面処理方法は特に限定されず、公知慣用の方法を用いればよく、硬化性反応基を有する表面処理剤、例えば、硬化性反応基を有するカップリング剤等で(D)無機フィラーの表面を処理すればよい。 The inorganic filler (D) is preferably a surface-treated inorganic filler. As the surface treatment, a surface treatment using a coupling agent or a surface treatment such as an alumina treatment that does not introduce an organic group may be performed. (D) The surface treatment method of the inorganic filler is not particularly limited, and a known and commonly used method may be used, and a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group, etc. (D) The surface of the inorganic filler may be treated.
(D)無機フィラーの表面処理は、カップリング剤による表面処理であることが好ましい。カップリング剤としては、シラン系、チタネート系、アルミネート系およびジルコアルミネート系等のカップリング剤が使用できる。中でもシラン系カップリング剤が好ましい。かかるシラン系カップリング剤の例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、N−(2−アミノメチル)−3−アミノプロピルメチルジメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、3−アニリノプロピルトリメトキシシラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−メルカプトプロピルトリメトキシシラン、N−フェニル−3−アミノプロピルトリメトキシシラン等を挙げることができ、これらは単独で、あるいは併用して使用することができる。これらのシラン系カップリング剤は、予め無機フィラーの表面に吸着あるいは反応により固定化されていることが好ましい。ここで、無機フィラー100質量部に対するカップリング剤の処理量は、例えば、0.1〜10質量部である。 The surface treatment of the inorganic filler (D) is preferably a surface treatment with a coupling agent. As the coupling agent, a silane-based, titanate-based, aluminate-based, zircoaluminate-based coupling agent or the like can be used. Of these, a silane coupling agent is preferable. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-amino. Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy) Cyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc. can be mentioned, which may be used alone or in combination. Can be used. These silane-based coupling agents are preferably immobilized on the surface of the inorganic filler in advance by adsorption or reaction. Here, the treatment amount of the coupling agent with respect to 100 parts by mass of the inorganic filler is, for example, 0.1 to 10 parts by mass.
硬化性反応基としては熱硬化性反応基が好ましい。熱硬化性反応基としては、水酸基、カルボキシル基、イソシアネート基、アミノ基、イミノ基、エポキシ基、オキセタニル基、メルカプト基、メトキシメチル基、メトキシエチル基、エトキシメチル基、エトキシエチル基、オキサゾリン基等が挙げられる。中でも、アミノ基およびエポキシ基のいずれか少なくとも1種が好ましい。なお、表面処理された無機フィラーは、熱硬化性反応基に加え、光硬化性反応基を有していてもよい。 As the curable reactive group, a thermosetting reactive group is preferable. Examples of the thermosetting reactive group include a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group and an oxazoline group. Can be mentioned. Of these, at least one of an amino group and an epoxy group is preferable. The surface-treated inorganic filler may have a photocurable reactive group in addition to the thermosetting reactive group.
なお、表面処理がされた無機フィラーは、表面処理された状態で硬化性樹脂組成物からの樹脂層に含有されていればよく、前記樹脂層を形成する硬化性樹脂組成物に無機フィラーと表面処理剤とを別々に配合して組成物中で無機フィラーが表面処理されてもよいが、予め表面処理した無機フィラーを配合することが好ましい。予め表面処理した無機フィラーを配合することによって、別々に配合した場合に残存しうる表面処理で消費されなかった表面処理剤によるクラック耐性等の低下を防ぐことができる。予め表面処理する場合は、溶剤や硬化性樹脂に無機フィラーを予備分散した予備分散液を配合することが好ましく、表面処理した無機フィラーを溶剤に予備分散し、該予備分散液を組成物に配合するか、表面未処理の無機フィラーを溶剤に予備分散する際に十分に表面処理した後、該予備分散液を組成物に配合することがより好ましい。 The surface-treated inorganic filler may be contained in the resin layer from the curable resin composition in the surface-treated state, and the curable resin composition forming the resin layer contains the inorganic filler and the surface. The inorganic filler may be surface-treated in the composition by separately blending the treatment agent, but it is preferable to blend the inorganic filler which has been surface-treated in advance. By blending the inorganic filler that has been surface-treated in advance, it is possible to prevent a decrease in crack resistance and the like due to the surface treatment agent that may remain when the inorganic filler is blended separately and is not consumed in the surface treatment. In the case of surface treatment in advance, it is preferable to mix a pre-dispersion liquid in which an inorganic filler is pre-dispersed in a solvent or a curable resin, and the surface-treated inorganic filler is pre-dispersed in a solvent and the pre-dispersion liquid is blended in the composition. It is more preferable that the surface-untreated inorganic filler is sufficiently surface-treated when it is pre-dispersed in a solvent, and then the pre-dispersion liquid is blended into the composition.
(D)無機フィラーは、粉体または固体状態でエポキシ樹脂等と配合してもよく、溶剤や分散剤と混合してスラリーとした後でエポキシ樹脂等と配合してもよい。 The inorganic filler (D) may be blended with an epoxy resin or the like in a powder or solid state, or may be mixed with a solvent or a dispersant to form a slurry and then blended with the epoxy resin or the like.
(D)無機フィラーは、1種を単独で用いてもよく、2種以上の混合物として用いてもよい。(D)無機フィラーの配合量は、樹脂組成物中の固形分を100質量%とした場合、低CTE化の観点から、50質量%以上が好ましく、60質量%以上がより好ましく、65質量%以上がさらに好ましい。また、硬化膜の靭性の観点から、90質量%以下が好ましく、80質量%以下がより好ましく、75質量%以下が特に好ましい。
なお、本明細書において、樹脂組成物中の固形分とは有機溶剤を除く成分を意味する。
The inorganic filler (D) may be used alone or as a mixture of two or more. When the solid content in the resin composition is 100% by mass, the blending amount of the inorganic filler (D) is preferably 50% by mass or more, more preferably 60% by mass or more, and 65% by mass from the viewpoint of reducing CTE. The above is more preferable. Further, from the viewpoint of toughness of the cured film, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 75% by mass or less is particularly preferable.
In the present specification, the solid content in the resin composition means a component excluding the organic solvent.
[熱可塑性樹脂]
本発明の硬化性樹脂組成物は、得られる硬化膜の機械的強度を向上させるために、さらに熱可塑性樹脂を含有することができる。熱可塑性樹脂は、溶剤に可溶であることが好ましい。溶剤に可溶である場合、ドライフィルム化した場合に柔軟性が向上し、クラックの発生や粉落ちを抑制できる。熱可塑性樹脂としては、熱可塑性ポリヒドロキシポリエーテル樹脂や、エピクロルヒドリンと各種2官能フェノール化合物の縮合物であるフェノキシ樹脂或いはその骨格に存在するヒドロキシエーテル部の水酸基を各種酸無水物や酸クロリドを使用してエステル化したフェノキシ樹脂、ポリビニルアセタール樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ブロック共重合体等が挙げられる。熱可塑性樹脂は1種を単独または2種以上を組み合わせて用いることができる。これら熱可塑性樹脂の中でも、誘電正接を低く維持したまま、ガラス転移温度を向上させることができるので、フェノキシ樹脂が好ましい。
[Thermoplastic resin]
The curable resin composition of the present invention may further contain a thermoplastic resin in order to improve the mechanical strength of the obtained cured film. The thermoplastic resin is preferably soluble in a solvent. When it is soluble in a solvent, its flexibility is improved when it is formed into a dry film, and the generation of cracks and powder falling can be suppressed. As the thermoplastic resin, various acid anhydrides or acid chlorides are used for the thermoplastic polyhydroxypolyether resin, the phenoxy resin which is a condensate of epichlorohydrin and various bifunctional phenol compounds, or the hydroxyl group of the hydroxyether portion existing in the skeleton thereof. Examples thereof include a phenoxy resin, a polyvinyl acetal resin, a polyamide resin, a polyamideimide resin, and a block copolymer that have been esterified. The thermoplastic resin may be used alone or in combination of two or more. Among these thermoplastic resins, a phenoxy resin is preferable because the glass transition temperature can be improved while maintaining a low dielectric loss tangent.
ポリビニルアセタール樹脂としては、例えば、ポリビニルアルコール樹脂をアルデヒドでアセタール化することで得られる。前記アルデヒドとしては、特に限定されず、例えば、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、アミルアルデヒド、ヘキシルアルデヒド、ヘプチルアルデヒド、2−エチルヘキシルアルデヒド、シクロヘキシルアルデヒド、フルフラール、ベンズアルデヒド、2−メチルベンズアルデヒド、3−メチルベンズアルデヒド、4−メチルベンズアルデヒド、p−ヒドロキシベンズアルデヒド、m−ヒドロキシベンズアルデヒド、フェニルアセトアルデヒド、β−フェニルプロピオンアルデヒド等が挙げられ、ブチルアルデヒドが好ましい。 The polyvinyl acetal resin can be obtained, for example, by acetalizing a polyvinyl alcohol resin with an aldehyde. The aldehyde is not particularly limited, and for example, formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, benzaldehyde, 2-methylbenzaldehyde, 3-. Examples thereof include methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde, and butylaldehyde is preferable.
フェノキシ樹脂の具体例としては、東都化成社製のFX280S、FX293、三菱ケミカル社製のjER(登録商標)YX8100BH30、jER(登録商標)YX6954BH30、YL6954、YL6974、jER(登録商標)YX7200B35等が挙げられる。また、ポリビニルアセタール樹脂の具体例としては、積水化学工業社製のエスレックKSシリーズ、ポリアミド樹脂としては、日立化成社製のKS5000シリーズ、日本化薬社製のBPシリーズ、さらに、ポリアミドイミド樹脂としては、日立化成社製のKS9000シリーズ等が挙げられる。熱可塑性樹脂の配合量は、樹脂組成物中の(A)窒素原子を含むエポキシ樹脂、(B)窒素原子を含まないエポキシ樹脂、および(C)活性エステル基を有する化合物の合計を100質量%とした場合、得られる硬化膜の機械的強度の観点から、0.1質量%以上が好ましく、0.3質量%以上がより好ましい。また、硬化膜の誘電特性の観点から、20質量%以下が好ましく、15質量%以下がより好ましい。 Specific examples of the phenoxy resin include FX280S and FX293 manufactured by Toto Kasei Co., Ltd., jER (registered trademark) YX8100BH30 manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) YX6954BH30, YL6954, YL6974, jER (registered trademark) YX7200B35 and the like. .. Specific examples of the polyvinyl acetal resin include the Eslek KS series manufactured by Sekisui Chemical Co., Ltd., the polyamide resin includes the KS5000 series manufactured by Hitachi Kasei Co., Ltd., the BP series manufactured by Nippon Kayaku Co., Ltd., and the polyamide-imide resin. , KS9000 series manufactured by Hitachi Kasei Co., Ltd. and the like. The blending amount of the thermoplastic resin is 100% by mass of the total of (A) an epoxy resin containing a nitrogen atom, (B) an epoxy resin containing no nitrogen atom, and (C) a compound having an active ester group in the resin composition. , 0.1% by mass or more is preferable, and 0.3% by mass or more is more preferable, from the viewpoint of the mechanical strength of the obtained cured film. Further, from the viewpoint of the dielectric property of the cured film, 20% by mass or less is preferable, and 15% by mass or less is more preferable.
[硬化促進剤]
本発明の硬化性樹脂組成物は、硬化促進剤を含有することができる。硬化促進剤は、熱硬化反応を促進させるものであり、密着性、耐薬品性、耐熱性等の特性をより一層向上させるために使用される。本発明において、硬化促進剤は、(A)窒素原子を含むエポキシ樹脂、(B)窒素原子を含まないエポキシ樹脂、および(C)活性エステル基を有する化合物の反応を主に促進させるために使用可能である。
[Curing accelerator]
The curable resin composition of the present invention can contain a curing accelerator. The curing accelerator accelerates the thermosetting reaction, and is used to further improve properties such as adhesion, chemical resistance, and heat resistance. In the present invention, the curing accelerator is mainly used to accelerate the reaction of (A) an epoxy resin containing a nitrogen atom, (B) an epoxy resin containing no nitrogen atom, and (C) a compound having an active ester group. It is possible.
(A)窒素原子を含むエポキシ樹脂および(B)窒素原子を含まないエポキシ樹脂と(C)活性エステル基を有する化合物等との硬化反応の硬化促進剤の具体例としては、イミダゾールおよびその誘導体;アセトグアナミン、ベンゾグアナミン等のグアナミン類;ジアミノジフェニルメタン、m−フェニレンジアミン、m−キシレンジアミン、ジアミノジフェニルスルフォン、ジシアンジアミド、尿素、尿素誘導体、メラミン、多塩基ヒドラジド等のポリアミン類;これらの有機酸塩および/またはエポキシアダクト;三フッ化ホウ素のアミン錯体;エチルジアミノ−S−トリアジン、2,4−ジアミノ−S−トリアジン、2,4−ジアミノ−6−キシリル−S−トリアジン等のトリアジン誘導体類;トリメチルアミン、トリエタノールアミン、N,N−ジメチルオクチルアミン、N−ベンジルジメチルアミン、ピリジン、ジメチルアミノピリジン、N−メチルモルホリン、ヘキサ(N−メチル)メラミン、2,4,6−トリス(ジメチルアミノフェノール)、テトラメチルグアニジン、m−アミノフェノール等のアミン類;ポリビニルフェノール、ポリビニルフェノール臭素化物、フェノールノボラック、アルキルフェノールノボラック等のポリフェノール類;トリブチルホスフィン、トリフェニルホスフィン、トリス−2−シアノエチルホスフィン等の有機ホスフィン類;トリ−n−ブチル(2,5−ジヒドロキシフェニル)ホスホニウムブロマイド、ヘキサデシルトリブチルホスホニウムクロライド等のホスホニウム塩類;ベンジルトリメチルアンモニウムクロライド、フェニルトリブチルアンモニウムクロライド等の4級アンモニウム塩類;前記多塩基酸無水物;ジフェニルヨードニウムテトラフルオロボロエート、トリフェニルスルホニウムヘキサフルオロアンチモネート、2,4,6−トリフェニルチオピリリウムヘキサフルオロホスフェート等の光カチオン重合触媒;スチレン−無水マレイン酸樹脂;フェニルイソシアネートとジメチルアミンの等モル反応物や、トリレンジイソシアネート、イソホロンジイソシアネート等の有機ポリイソシアネートとジメチルアミンの等モル反応物、金属触媒等の従来公知の硬化促進剤が挙げられる。硬化促進剤の中でも、イミダゾールおよびその誘導体、ジメチルアミノピリジンが好ましく、より高Tgかつ低誘電正接の硬化物が得られることから、ジメチルアミノピリジンがより好ましい。 Specific examples of the curing accelerator for the curing reaction between (A) an epoxy resin containing a nitrogen atom, (B) an epoxy resin containing no nitrogen atom, and (C) a compound having an active ester group include imidazole and a derivative thereof; Guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylene diamine, diaminodiphenyl sulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide; these organic acid salts and / Or epoxy adduct; amine complex of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine; trimethylamine, Triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, dimethylaminopyridine, N-methylmorpholin, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), Amines such as tetramethylguanidine and m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac and alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine; Phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; Photocationic polymerization catalysts such as iodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate; styrene-maleic anhydride resin; equimolar of phenylisocyanate and dimethylamine Examples thereof include reactants, equimolar reactants of organic polyisocyanates such as tolylene diisocyanate and isophorone diisocyanate and dimethylamine, and conventionally known curing accelerators such as metal catalysts. Among the curing accelerators, imidazole and its derivative, dimethylaminopyridine are preferable, and dimethylaminopyridine is more preferable because a cured product having a higher Tg and a low dielectric loss tangent can be obtained.
硬化促進剤は、1種を単独または2種以上混合して用いることができる。硬化促進剤が本発明の硬化性樹脂組成物に配合される場合、その配合量は、(A)〜(C)成分の合計量を100質量%とした場合、熱硬化反応前の樹脂組成物の保存安定性の観点から、5質量%以下が好ましく、3質量%以下がより好ましい、また、硬化性の観点から、0.01質量%以上が好ましく、0.1質量%以上がより好ましい。 The curing accelerator may be used alone or in combination of two or more. When the curing accelerator is blended in the curable resin composition of the present invention, the blending amount thereof is the resin composition before the thermosetting reaction when the total amount of the components (A) to (C) is 100% by mass. From the viewpoint of storage stability, 5% by mass or less is preferable, 3% by mass or less is more preferable, and from the viewpoint of curability, 0.01% by mass or more is preferable, and 0.1% by mass or more is more preferable.
[ゴム状粒子]
本発明の硬化性樹脂組成物は、必要に応じてゴム状粒子を含有することができる。このようなゴム状粒子としては、ポリブタジエンゴム、ポリイソプロピレンゴム、ウレタン変性ポリブタジエンゴム、エポキシ変性ポリブタジエンゴム、アクリロニトリル変性ポリブタジエンゴム、カルボキシル基変性ポリブタジエンゴム、カルボキシル基または水酸基で変性したアクリロニトリルブタジエンゴム、およびそれらの架橋ゴム粒子、コアシェル型ゴム粒子等が挙げられ、1種を単独または2種以上を組み合わせて用いることができる。これらのゴム状粒子は、得られる硬化膜の柔軟性を向上させたり、クラック耐性が向上したり、酸化剤による表面粗化処理を可能とし、銅箔等との密着強度を向上させるために添加される。
[Rubber-like particles]
The curable resin composition of the present invention may contain rubber-like particles, if necessary. Examples of such rubber-like particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl group-modified polybutadiene rubber, carboxyl group-modified or hydroxyl-modified acrylonitrile-butadiene rubber, and Examples thereof include crosslinked rubber particles and core-shell type rubber particles, and one type can be used alone or in combination of two or more types. These rubber-like particles are added to improve the flexibility of the obtained cured film, improve crack resistance, enable surface roughness treatment with an oxidizing agent, and improve the adhesion strength with copper foil and the like. Will be done.
ゴム状粒子の平均粒子径は0.005〜1μmの範囲が好ましく、0.2〜1μmの範囲がより好ましい。本発明におけるゴム状粒子の平均粒子径は、レーザー回折式粒子径分布測定装置により求めることができる。例えば、適当な有機溶剤にゴム状粒子を超音波などにより均一に分散させ、マイクロトラック・ベル社製Nanotrac waveを用いて、ゴム状粒子の粒度分布を質量基準で作成し、そのメディアン径を平均粒子径とすることで測定することができる。 The average particle size of the rubber-like particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 1 μm. The average particle size of the rubber-like particles in the present invention can be determined by a laser diffraction type particle size distribution measuring device. For example, rubber-like particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and a particle size distribution of the rubber-like particles is prepared on a mass basis using Nanotrac wave manufactured by Microtrac Bell, and the median diameters thereof are averaged. It can be measured by setting the particle size.
[難燃剤]
本発明の硬化性樹脂組成物は、難燃剤を含有することができる。難燃剤としては、水酸化アルミニウム、水酸化マグネシウム等の水和金属系、赤燐、燐酸アンモニウム、炭酸アンモニウム、ホウ酸亜鉛、錫酸亜鉛、モリブデン化合物系、臭素化合物系、塩素化合物系、燐酸エステル、含燐ポリオール、含燐アミン、メラミンシアヌレート、メラミン化合物、トリアジン化合物、グアニジン化合物、シリコンポリマー等が使用できる。難燃剤は、1種を単独または2種以上を組み合わせて用いることができる。
[Flame retardants]
The curable resin composition of the present invention can contain a flame retardant. Flame retardants include hydrated metals such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc nitrate, molybdenum compound, bromine compound, chlorine compound, and phosphoric acid ester. , Phosphoric acid-containing polyol, phosphorus-containing amine, melamine cyanurate, melamine compound, triazine compound, guanidine compound, silicon polymer and the like can be used. The flame retardant may be used alone or in combination of two or more.
[有機溶剤]
有機溶剤としては、特に制限はないが、例えば、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などが挙げることができる。より具体的には、メチルエチルケトン、シクロヘキサノン、メチルブチルケトン、メチルイソブチルケトン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、酢酸イソブチル、エチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのエステル類;エタノール、プロパノール、2−メトキシプロパノール、n−ブタノール、イソブチルアルコール、イソペンチルアルコール、エチレングリコール、プロピレングリコール等のアルコール類;オクタン、デカン等の脂肪族炭化水素;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤等の他、N,N−ジメチルホルムアミド(DMF)、テトラクロロエチレン、テレビン油等が挙げられる。また、丸善石油化学社製スワゾール1000、スワゾール1500、三共化学社製ソルベント#100、ソルベント#150、シェルケミカルズジャパン社製シェルゾールA100、シェルゾールA150、出光興産社製イプゾール100番、イプゾール150番等の有機溶剤を用いてもよい。有機溶剤は、1種を単独または2種以上を組み合わせて用いることができる。
[Organic solvent]
The organic solvent is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. it can. More specifically, ketones such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol and methyl carbitol. , Butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; Esters such as ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; ethanol, propanol, 2- Alcohols such as methoxypropanol, n-butanol, isobutyl alcohol, isopentyl alcohol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. In addition to system solvents and the like, N, N-dimethylformamide (DMF), tetrachloroethylene, televisionne oil and the like can be mentioned. In addition, Maruzen Petrochemical Co., Ltd. Swazol 1000, Swazole 1500, Sankyo Chemical Co., Ltd. Solvent # 100, Solvent # 150, Shell Chemicals Japan Co., Ltd. Shellsol A100, Shellsol A150, Idemitsu Kosan Co., Ltd. You may use the organic solvent of. As the organic solvent, one type can be used alone or two or more types can be used in combination.
ドライフィルム化した場合、樹脂層中の残留溶剤量が、0.1〜10.0質量%であることが好ましくい。残留溶剤が10.0質量%以下であると、熱硬化時の突沸を抑え、表面の平坦性がより良好となる。また、溶融粘度が下がり過ぎて樹脂が流れてしまうことを抑制でき、平坦性が良好となる。残留溶剤が0.1質量%以上であると、ラミネート時の流動性が良好で、平坦性および埋め込み性がより良好となる。 When formed into a dry film, the amount of residual solvent in the resin layer is preferably 0.1 to 10.0% by mass. When the residual solvent is 10.0% by mass or less, bumping during thermosetting is suppressed and the flatness of the surface becomes better. Further, it is possible to prevent the resin from flowing due to the melt viscosity being lowered too much, and the flatness is improved. When the residual solvent is 0.1% by mass or more, the fluidity at the time of laminating is good, and the flatness and the embedding property are more good.
[その他の成分]
本発明の硬化性樹脂組成物は、さらに必要に応じて、シリコンパウダー、フッ素パウダー、ナイロンパウダー等の有機フィラー、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラック等の従来公知の着色剤、アスベスト、オルベン、ベントン、微紛シリカ等の従来公知の増粘剤、シリコーン系、フッ素系、高分子系等の消泡剤および/またはレベリング剤、チアゾール系、トリアゾール系、シランカップリング剤等の密着性付与剤、チタネート系、アルミニウム系の従来公知の添加剤類を用いることができる。
[Other ingredients]
The curable resin composition of the present invention further comprises organic fillers such as silicon powder, fluorine powder, nylon powder, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, as required. Conventionally known colorants such as carbon black and naphthalene black, conventionally known thickeners such as asbestos, orben, benton, and fine powder silica, silicone-based, fluorine-based, and polymer-based defoamers and / or leveling agents. , Thiazol-based, Triazole-based, Adhesion-imparting agents such as silane coupling agents, and titanate-based and aluminum-based conventionally known additives can be used.
本発明の硬化性樹脂組成物は、ドライフィルム化して用いても液状として用いても良い。液状として用いる場合は、1液性でも2液性以上でもよいが、保存安定性の観点から2液性以上であることが好ましい。 The curable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more, but it is preferably two-component or more from the viewpoint of storage stability.
<ドライフィルム>
本発明のドライフィルムは、本発明の硬化性樹脂組成物をキャリアフィルム上に塗布し、乾燥して、乾燥塗膜としての樹脂層を形成することにより、製造することができる。樹脂層上には、必要に応じて、保護フィルムをラミネートすることができる。
<Dry film>
The dry film of the present invention can be produced by applying the curable resin composition of the present invention on a carrier film and drying it to form a resin layer as a dry coating film. A protective film can be laminated on the resin layer, if necessary.
キャリアフィルムとは、ドライフィルムの樹脂層を支持する役割を有するものであり、該樹脂層を形成する際に、硬化性樹脂組成物が塗布されるフィルムである。キャリアフィルムとしては、例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステルフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等の熱可塑性樹脂からなるフィルム、および、表面処理した紙等を用いることができる。これらの中でも、耐熱性、機械的強度、取扱性等の観点から、ポリエステルフィルムを好適に使用することができる。キャリアフィルムの厚さは、特に制限されるものではないが概ね10〜150μmの範囲で用途に応じて適宜選択される。キャリアフィルムの樹脂層を設ける面には、離型処理が施されていてもよい。また、キャリアフィルムの樹脂層を設ける面には、スパッタもしくは銅箔が形成されていてもよい。 The carrier film has a role of supporting the resin layer of the dry film, and is a film to which the curable resin composition is applied when the resin layer is formed. Examples of the carrier film include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polyethylene films, polytetrafluoroethylene films, polypropylene films, and films made of thermoplastic resins such as polystyrene films. Surface-treated paper or the like can be used. Among these, a polyester film can be preferably used from the viewpoints of heat resistance, mechanical strength, handleability and the like. The thickness of the carrier film is not particularly limited, but is appropriately selected in the range of approximately 10 to 150 μm according to the application. The surface of the carrier film on which the resin layer is provided may be subjected to a mold release treatment. Further, sputter or copper foil may be formed on the surface of the carrier film on which the resin layer is provided.
保護フィルムとは、ドライフィルムの樹脂層の表面に塵等が付着するのを防止するとともに取扱性を向上させる目的で、樹脂層のキャリアフィルムとは反対の面に設けられる。保護フィルムとしては、例えば、前記キャリアフィルムで例示した熱可塑性樹脂からなるフィルム、および、表面処理した紙等を用いることができるが、これらの中でも、ポリエステルフィルムおよびポリエチレンフィルム、ポリプロピレンフィルムが好ましい。保護フィルムの厚さは、特に制限されるものではないが概ね10〜150μmの範囲で用途に応じて適宜選択される。保護フィルムの樹脂層を設ける面には、離型処理が施されていてもよい。 The protective film is provided on the surface opposite to the carrier film of the resin layer for the purpose of preventing dust and the like from adhering to the surface of the resin layer of the dry film and improving handleability. As the protective film, for example, a film made of the thermoplastic resin exemplified in the carrier film, surface-treated paper and the like can be used, and among these, a polyester film, a polyethylene film and a polypropylene film are preferable. The thickness of the protective film is not particularly limited, but is appropriately selected in the range of approximately 10 to 150 μm according to the application. The surface of the protective film on which the resin layer is provided may be subjected to a mold release treatment.
<樹脂付き銅箔>
本発明の樹脂付き銅箔は、本発明の硬化性樹脂組成物を銅箔またはキャリア付き銅箔の銅箔面に塗布、乾燥して得られる樹脂層を有する。
<Copper foil with resin>
The resin-containing copper foil of the present invention has a resin layer obtained by applying the curable resin composition of the present invention to the copper foil surface of a copper foil or a copper foil with a carrier and drying it.
[キャリア付き銅箔]
キャリア付き銅箔は、キャリア箔および銅箔をこの順に備えた構成であればよく、本発明の硬化性樹脂組成物からなる樹脂層は、銅箔と接するように積層されていればよい。銅箔としては極薄銅箔を用いることが好ましい。
[Copper foil with carrier]
The copper foil with a carrier may have a structure in which the carrier foil and the copper foil are provided in this order, and the resin layer made of the curable resin composition of the present invention may be laminated so as to be in contact with the copper foil. It is preferable to use an ultrathin copper foil as the copper foil.
キャリア箔としては、銅箔、アルミニウム箔、ステンレス(SUS)箔、表面をメタルコーティングした樹脂フィルム等が挙げられ、銅箔であることが好ましい。銅箔は、電解銅箔でも圧延銅箔でもよい。キャリア箔の厚さは、通常は250μm以下であり、好ましくは9〜200μmである。なお、キャリア箔と銅箔との間に、必要に応じて剥離層を形成してもよい。 Examples of the carrier foil include copper foil, aluminum foil, stainless steel (SUS) foil, and a resin film having a metal-coated surface, and copper foil is preferable. The copper foil may be an electrolytic copper foil or a rolled copper foil. The thickness of the carrier foil is usually 250 μm or less, preferably 9 to 200 μm. A release layer may be formed between the carrier foil and the copper foil, if necessary.
銅箔の形成方法は特に限定されないが、極薄銅箔とすることが好ましく、無電解銅めっき法、電解銅めっき法等の湿式成膜法、スパッタリング、化学蒸着等の乾式成膜法、また、これらの組合せにより形成することができる。極薄銅箔の厚さは、0.1〜7.0μmであることが好ましく、0.5〜5.0μmであることがより好ましく、1.0〜3.0μmであることがさらに好ましい。 The method for forming the copper foil is not particularly limited, but an ultrathin copper foil is preferable, and a wet film forming method such as an electrolytic copper plating method and an electrolytic copper plating method, a dry film forming method such as sputtering and chemical vapor deposition, and a dry film forming method such as sputtering and chemical vapor deposition, and , Can be formed by a combination of these. The thickness of the ultrathin copper foil is preferably 0.1 to 7.0 μm, more preferably 0.5 to 5.0 μm, and even more preferably 1.0 to 3.0 μm.
<硬化物>
本発明の硬化物は、本発明の硬化性樹脂組成物、本発明のドライフィルムの樹脂層、又は本発明の樹脂付き銅箔の樹脂層を硬化して得られる。
<Cured product>
The cured product of the present invention is obtained by curing the curable resin composition of the present invention, the resin layer of the dry film of the present invention, or the resin layer of the copper foil with resin of the present invention.
硬化する方法は特に限定されず、従来公知の方法で硬化させればよく、例えば、150〜230℃で加熱して硬化すればよい。硬化性樹脂組成物を用いたプリント配線板の製造方法としては、例えば、キャリアフィルムと保護フィルムとの間に樹脂層が挟まれた三層構造のドライフィルムの場合、下記のような方法でプリント配線板を製造することができる。ドライフィルムからキャリアフィルムまたは保護フィルムのどちらかを剥離し、回路パターンが形成された回路基板に加熱ラミネートした後、熱硬化させる。熱硬化は、オーブン中で硬化、もしくは熱板プレスで硬化させてもよい。回路が形成された基材と本発明のドライフィルムをラミネートもしくは熱板プレスする際に、銅箔もしくは回路形成された基材を同時に積層することもできる。回路パターンが形成された基板上の所定の位置に対応する位置に、レーザー照射またはドリルでパターンやビアホールを形成し、回路配線を露出させることで、プリント配線板を製造することができる。この際、パターンやビアホール内の回路配線上に除去しきれないで残留した成分(スミア)が存在する場合にはデスミア処理を行う。キャリアフィルムまたは保護フィルムのうち残った方は、ラミネート後、熱硬化後、レーザー加工後またはデスミア処理後のいずれかに、剥離すればよい。 The method of curing is not particularly limited, and it may be cured by a conventionally known method, for example, it may be cured by heating at 150 to 230 ° C. As a method for manufacturing a printed wiring board using a curable resin composition, for example, in the case of a dry film having a three-layer structure in which a resin layer is sandwiched between a carrier film and a protective film, printing is performed by the following method. A wiring board can be manufactured. Either the carrier film or the protective film is peeled off from the dry film, heat-laminated on the circuit board on which the circuit pattern is formed, and then thermosetting. The thermosetting may be cured in an oven or may be cured by a hot plate press. When laminating or hot plate pressing the base material on which the circuit is formed and the dry film of the present invention, the copper foil or the base material on which the circuit is formed can be laminated at the same time. A printed wiring board can be manufactured by forming a pattern or a via hole by laser irradiation or a drill at a position corresponding to a predetermined position on a substrate on which a circuit pattern is formed to expose the circuit wiring. At this time, if there is a residual component (smear) that cannot be completely removed on the pattern or the circuit wiring in the via hole, the desmear treatment is performed. The remaining carrier film or protective film may be peeled off either after laminating, after thermosetting, after laser processing, or after desmear treatment.
また、本発明の樹脂付き銅箔を用いてプリント配線板を製造する場合、樹脂層を回路パターンが形成された回路基板に積層し、銅箔を配線層の全部または一部としてモディファイド・セミアディティブプロセス(MSAP)法で回路を形成し、ビルドアップ配線板を製造してもよい。また、銅箔を除去してセミアディティブプロセス(SAP)法で回路を形成したビルドアップ配線板を製造してもよい。また、半導体集積回路上へ樹脂付銅箔の積層と回路形成を交互に繰りかえすダイレクト・ビルドアップ・オン・ウェハーでプリント配線板を製造してもよい。また、コア基板を用いずに、樹脂層と導体層とが交互に積層されたコアレスビルドアップ法を用いてもよい。 Further, when a printed wiring board is manufactured using the copper foil with resin of the present invention, the resin layer is laminated on the circuit board on which the circuit pattern is formed, and the copper foil is modified and semi-additive as all or part of the wiring layer. A circuit may be formed by a process (MSAP) method to manufacture a build-up wiring board. Further, a build-up wiring board in which a circuit is formed by a semi-additive process (SAP) method may be manufactured by removing the copper foil. Further, the printed wiring board may be manufactured by a direct build-up on wafer in which the lamination of the copper foil with resin and the circuit formation are alternately repeated on the semiconductor integrated circuit. Further, instead of using a core substrate, a coreless build-up method in which resin layers and conductor layers are alternately laminated may be used.
<電子部品>
本発明の電子部品は、本発明の硬化物、すなわち、本発明の硬化性樹脂組成物、本発明のドライフィルムの樹脂層、又は本発明の樹脂付き銅箔の樹脂層の硬化物を有する。
電子部品としては、例えば、プリント配線板の永久保護膜が挙げられ、中でもソルダーレジスト層、層間絶縁層、フレキシブルプリント配線板のカバーレイが挙げられる。また、プリント配線板以外の用途、例えば、インダクタなどの受動部品も電子部品に含まれる。
<Electronic components>
The electronic component of the present invention has a cured product of the present invention, that is, a cured resin composition of the present invention, a resin layer of a dry film of the present invention, or a cured product of a resin layer of a copper foil with a resin of the present invention.
Examples of the electronic component include a permanent protective film of a printed wiring board, and among them, a solder resist layer, an interlayer insulating layer, and a coverlay of a flexible printed wiring board. In addition, electronic components include applications other than printed wiring boards, for example, passive components such as inductors.
本発明の硬化性樹脂組成物は、上述の用途以外に、プリント配線板の永久穴埋め、例えば、スルーホールやビアホール等の穴埋めにも好適に用いることができる。また、半導体チップ用の封止材や、銅張積層板(CCL)やプリプレグの材料としても用いることができる。 The curable resin composition of the present invention can be suitably used for filling permanent holes in printed wiring boards, for example, filling holes such as through holes and via holes, in addition to the above-mentioned uses. It can also be used as a sealing material for semiconductor chips, as a material for copper-clad laminates (CCL) and prepregs.
また、本発明の硬化性樹脂組成物の硬化物は誘電特性に優れることから、これを用いることにより高周波用途においても伝送品質が良好とされる。高周波用途の具体例としては、例えば、自動運転向けミリ波レーダーやミリ波センサー用基板、高速通信対応モバイル用マザーボードやモディファイド・セミアディティブプロセス(MSAP)法で回路を形成するSLP(Substrate−Like PCB)、モバイルおよびパソコン用アプリケーションプロセッサ(AP)、基地局用サーバーやルーター向け高多層基板、アンテナ向け基板や半導体封止材料などが挙げられる。 Further, since the cured product of the curable resin composition of the present invention has excellent dielectric properties, it is considered that the transmission quality is good even in high frequency applications by using the cured product. Specific examples of high-frequency applications include millimeter-wave radars for automatic operation, millimeter-wave sensor substrates, high-speed communication-compatible mobile motherboards, and SLPs (Substation-Like PCBs) that form circuits using the Modified Semi-Additive Process (MSAP) method. ), Application processors (APs) for mobile and personal computers, high-frequency substrates for base station servers and routers, substrates for antennas, semiconductor encapsulation materials, and the like.
さらに、本発明のドライフィルムを用いて、配線を貼り合わせることによって配線板を形成してもよい。 Further, the wiring board may be formed by bonding the wirings using the dry film of the present invention.
本発明の硬化性樹脂組成物を用いた回路形成材料の形態は、モディファイド・セミアディティブプロセス(MSAP)対応の樹脂付き銅箔(RCC:Resin−Coated−Copper)やセミアディティブプロセス(SAP)対応のビルドアップフィルムであってもよい。 The form of the circuit forming material using the curable resin composition of the present invention is compatible with modified semi-additive process (MSAP) -compatible copper foil with resin (RCC: Resin-Coated-Copper) and semi-additive process (SAP). It may be a build-up film.
本発明の硬化物の誘電正接は特に限定されないが、本発明によれば低い誘電正接の硬化物を得ることが可能であり、例えば、周波数10GHz、23℃にて、0.003以下、さらには0.002以下、またさらには0.001以下とすることも可能である。 The dielectric loss tangent of the cured product of the present invention is not particularly limited, but according to the present invention, a cured product having a low dielectric loss tangent can be obtained. It can be 0.002 or less, and even 0.001 or less.
以下、実施例を示して本発明について具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、以下において特に断りのない限り、「部」、「%」は、質量部、質量%を意味するものとする。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following, unless otherwise specified, "parts" and "%" mean parts by mass and% by mass.
((C)活性エステル基を有する化合物の合成)
[合成例1]
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにイソフタル酸クロリド 203.0g(酸クロリド基のモル数:2.0モル)とトルエン 1338gを仕込み系内を減圧窒素置換し溶解させた。次いで、α−ナフトール96.0g(0.67モル)、ジシクロペンタジエンフェノール樹脂220g(フェノール性水酸基のモル数:1.33モル)を仕込み、系内を減圧窒素置換し溶解させた。その後、テトラブチルアンモニウムブロマイド 1.12gを溶解させ、窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液400gを3時間かけて滴下した。次いでこの条件下で1.0時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているトルエン相に水を投入して約15分間撹拌混合し、静置分液して水層を取り除いた。水層のpHが7になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去し固形分65%のトルエン溶液状態にある活性エステル基を有する化合物(C−1)を得た。
得られた活性エステル基を有する化合物(C−1)の固形分換算のエステル基当量は223g/molであった。
((C) Synthesis of compound having active ester group)
[Synthesis Example 1]
203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1338 g of toluene were charged in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure. And dissolved. Next, 96.0 g (0.67 mol) of α-naphthol and 220 g of dicyclopentadienephenol resin (number of moles of phenolic hydroxyl group: 1.33 mol) were charged, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve it. Then, 1.12 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the inside of the system was controlled to 60 ° C. or lower, and 400 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Then, stirring was continued for 1.0 hour under this condition. After completion of the reaction, the liquid was separated by standing and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the solution was allowed to separate to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, water was removed by decanter dehydration to obtain a compound (C-1) having an active ester group in a toluene solution with a solid content of 65%.
The solid content-equivalent ester group equivalent of the obtained compound (C-1) having an active ester group was 223 g / mol.
[合成例2]
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコに、2,7−ジヒドロキシナフタレン 320g(2.0モル)、ベンジルアルコール 184g(1.7モル)、パラトルエンスルホン酸・1水和物 5.0gを仕込み、室温下、窒素を吹き込みながら撹拌した。その後、150℃に昇温し、生成する水を系外に留去しながら4時間攪拌した。反応終了後、メチルイソブチルケトン 900g、20%水酸化ナトリウム水溶液 5.4gを添加して中和した後、分液により水層を除去し、水280gで3回水洗を行い、メチルイソブチルケトンを減圧下除去してベンジル変性ナフタレン化合物(C−2中間体)を460g得た。得られたベンジル変性ナフタレン化合物(C−2中間体)は黒色固体であり、水酸基当量は180グラム/当量であった。
次いで、温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けた別のフラスコに、イソフタル酸クロリド 203.0g(酸クロリド基のモル数:2.0モル)とトルエン 1400gを仕込み、系内を減圧窒素置換し溶解させた。次いで、α−ナフトール 96.0g(0.67モル)、ベンジル変性ナフタレン化合物(B−2中間体) 240g(フェノール性水酸基のモル数:1.33モル)を仕込み、系内を減圧窒素置換し溶解させた。その後、テトラブチルアンモニウムブロマイド 0.70gを溶解させ、窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液 400gを3時間かけて滴下した。次いでこの条件下で1.0時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているトルエン層に水を投入して15分間撹拌混合し、静置分液して水層を取り除いた。水層のpHが7になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去し固形分65質量%のトルエン溶液状態にある活性エステル基を有する化合物(C−2)を得た。得られた活性エステル基を有する化合物(C−2)の固形分換算のエステル基当量は230g/molであった。
[Synthesis Example 2]
320 g (2.0 mol) of 2,7-dihydroxynaphthalene, 184 g (1.7 mol) of benzyl alcohol, paratoluenesulfonic acid in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 5.0 g of monohydrate was charged, and the mixture was stirred at room temperature while blowing nitrogen. Then, the temperature was raised to 150 ° C., and the generated water was stirred for 4 hours while being distilled off from the system. After completion of the reaction, 900 g of methyl isobutyl ketone and 5.4 g of a 20% aqueous sodium hydroxide solution were added to neutralize the mixture, the aqueous layer was removed by liquid separation, and the mixture was washed with 280 g of water three times to reduce the pressure of methyl isobutyl ketone. The bottom was removed to obtain 460 g of a benzyl-modified naphthalene compound (C-2 intermediate). The obtained benzyl-modified naphthalene compound (C-2 intermediate) was a black solid and had a hydroxyl group equivalent of 180 g / equivalent.
Next, 203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1400 g of toluene were charged in another flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. The inside of the system was replaced with reduced pressure nitrogen to dissolve it. Next, 96.0 g (0.67 mol) of α-naphthol and 240 g (molar number of phenolic hydroxyl groups: 1.33 mol) of the benzyl-modified naphthalene compound (B-2 intermediate) were charged, and the inside of the system was replaced with nitrogen under reduced pressure. It was dissolved. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the temperature inside the system was controlled to 60 ° C. or lower, and 400 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Then, stirring was continued for 1.0 hour under this condition. After completion of the reaction, the liquid was separated by standing and the aqueous layer was removed. Further, water was added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred and mixed for 15 minutes, and the solution was allowed to be separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, water was removed by decanter dehydration to obtain a compound (C-2) having an active ester group in a toluene solution with a solid content of 65% by mass. The solid content-equivalent ester group equivalent of the obtained compound (C-2) having an active ester group was 230 g / mol.
<1.実施例1〜13および比較例1〜3の硬化性樹脂組成物の調製>
下記表1の実施例、比較例に示す種々の成分と共に表1に示す割合(質量部)にて混錬混合し、硬化後フィルム作製用の硬化性樹脂組成物を調製した。なお、表中の数値は質量部(固形分換算)を示す。
前記各硬化性樹脂組成物について、以下に示すように、試験用試料を作成し、ガラス転移温度(Tg)、誘電正接、及びピール強度の評価を行った。その結果を表1に示す。
<1. Preparation of curable resin compositions of Examples 1 to 13 and Comparative Examples 1 to 3>
A curable resin composition for producing a film after curing was prepared by kneading and mixing with various components shown in Examples and Comparative Examples in Table 1 below at a ratio (part by mass) shown in Table 1. The numerical values in the table indicate parts by mass (in terms of solid content).
As shown below, test samples were prepared for each of the curable resin compositions, and the glass transition temperature (Tg), dielectric loss tangent, and peel strength were evaluated. The results are shown in Table 1.
<硬化後フィルムの作製>
フィルムアプリケーターを用いて、硬化性樹脂組成物を実施例および比較例ごとに銅箔(古河電気工業社製F2−WS、18μm厚)の光沢面上に塗布し、熱風循環式乾燥炉にて90℃で10分間乾燥後、続けて200℃で60分間硬化させた後、銅箔を剥離し、厚み約40μmの硬化後フィルム(硬化膜)を作製した。
<Preparation of film after curing>
Using a film applicator, a curable resin composition was applied to the glossy surface of a copper foil (F2-WS manufactured by Furukawa Electric Co., Ltd., 18 μm thickness) for each example and comparative example, and 90 in a hot air circulation type drying oven. After drying at ° C. for 10 minutes and then curing at 200 ° C. for 60 minutes, the copper foil was peeled off to prepare a cured film (cured film) having a thickness of about 40 μm.
<ガラス転移温度(Tg)の測定>
前記<硬化後フィルムの作製>で得られたサンプルを測定サイズ(3mm×10mmのサイズ)に切り出し、ティー・エイ・インスツルメント社製TMA Q400EMを用いて、ガラス転移温度(Tg)を測定した。10℃/minの昇温速度で室温より昇温、連続して2回測定し、2回目における線熱膨張係数の異なる2接線の交点であるガラス転移温度(Tg)を下記の基準で評価した。
◎:175℃以上
○:175℃未満〜170℃以上
×:170℃未満
−:得られる硬化物が脆い為、強度不足により測定不可
<Measurement of glass transition temperature (Tg)>
The sample obtained in the above <Preparation of film after curing> was cut out to a measurement size (size of 3 mm × 10 mm), and the glass transition temperature (Tg) was measured using TMA Q400EM manufactured by TA Instruments. .. The temperature was raised from room temperature at a rate of 10 ° C./min, and the temperature was measured twice in succession, and the glass transition temperature (Tg), which is the intersection of two tangents with different linear thermal expansion coefficients, was evaluated according to the following criteria. ..
⊚: 175 ° C or higher
◯: Less than 175 ° C to 170 ° C or higher ×: Less than 170 ° C −: Since the obtained cured product is brittle, measurement is not possible due to insufficient strength.
<誘電正接(Df)の測定>
前記<硬化後フィルムの作製>で得られたサンプルを測定サイズ(50mm×60mmのサイズ)に切り出し、SPDR誘電体共振器とネットワークアナライザー(ともにアジレント社製)を用い、23℃における10GHzの誘電正接の測定を行い、下記の基準で評価した。
◎:0.003未満
○:0.003以上〜0.005未満
×:0.005以上
−:得られる硬化物が脆い為、強度不足により測定不可
<Measurement of dielectric loss tangent (Df)>
The sample obtained in the above <Preparation of film after curing> was cut out to a measurement size (size of 50 mm × 60 mm), and a dielectric loss tangent of 10 GHz at 23 ° C. was used using an SPDR dielectric resonator and a network analyzer (both manufactured by Agilent). Was measured and evaluated according to the following criteria.
⊚: less than 0.003 ○: 0.003 or more to less than 0.005 ×: 0.005 or more −: Since the obtained cured product is brittle, measurement is not possible due to insufficient strength.
<ピール強度測定用サンプルの作製>
(1)積層板の粗化処理
内層回路の形成されたガラス布基材エポキシ樹脂両面銅張積層板[銅箔の厚さ18μm、基板厚み0.3mm、パナソニック社製R5715ES]の両面をメック社製CZ8100に浸漬して銅表面の粗化処理(エッチング量:約1μm)を行った。
(2)樹脂付き銅箔の作製
フィルムアプリケーターを用いて、硬化性樹脂組成物を各実施例および比較例ごとにキャリア付き極薄銅箔(三井金属社製MT18Ex、極薄銅3μm厚)の極薄銅箔面上に塗布し、熱風循環式乾燥炉にて90℃で10分間乾燥し、樹脂層の厚み約40μmの樹脂付き銅箔を得た。
(3)樹脂付き銅箔のラミネート
バッチ式真空加圧ラミネーターMVLP−500(名機製作所社製)を用いて、粗化処理(1)を行った積層板の両面に、樹脂付き銅箔(2)の樹脂組成物塗工面をラミネートした。ラミネートは、30秒間減圧して気圧を13hPa以下とし、その後30秒間、80℃、圧力0.5MPaでプレスすることにより行った。
(4)樹脂組成物の硬化
樹脂付き銅箔をラミネートした積層板(3)を、熱風循環式乾燥炉にて170℃で30分間、硬化させた。
(5)電解銅めっき
硬化後、積層板の両面からキャリア銅箔を剥離し、電解銅めっきにより、両面の極薄銅箔(3μm)を約25μm厚にした。
(6)アニール処理
電解銅めっき後の積層板を、熱風循環式乾燥炉にて200℃で60分間、アニール処理を行った。
<Preparation of sample for peel strength measurement>
(1) Roughening treatment of laminated board Mech Co., Ltd. on both sides of a glass cloth base material epoxy resin double-sided copper-clad laminated board [copper foil thickness 18 μm, substrate thickness 0.3 mm, Panasonic R5715ES] on which an inner layer circuit is formed. The copper surface was roughened (etching amount: about 1 μm) by immersing it in CZ8100 manufactured by Japan.
(2) Preparation of Copper Foil with Resin Using a film applicator, a curable resin composition was applied to each Example and Comparative Example of ultra-thin copper foil with a carrier (MT18Ex manufactured by Mitsui Kinzoku Co., Ltd., ultra-thin copper 3 μm thick). It was applied onto the thin copper foil surface and dried in a hot air circulation type drying furnace at 90 ° C. for 10 minutes to obtain a resin-coated copper foil having a resin layer thickness of about 40 μm.
(3) Lamination of Copper Foil with Resin Using a batch type vacuum pressurizing laminator MVLP-500 (manufactured by Meiki Co., Ltd.), copper foil with resin (2) was applied to both sides of the laminated board subjected to the roughening treatment (1). ) Resin composition coated surface was laminated. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 80 ° C. and a pressure of 0.5 MPa for 30 seconds.
(4) Curing of Resin Composition A laminated plate (3) laminated with a copper foil with a resin was cured at 170 ° C. for 30 minutes in a hot air circulation type drying oven.
(5) Electrolytic copper plating After curing, the carrier copper foil was peeled off from both sides of the laminated plate, and the ultrathin copper foil (3 μm) on both sides was made about 25 μm thick by electrolytic copper plating.
(6) Annealing Treatment The laminated plate after electrolytic copper plating was annealed in a hot air circulation type drying oven at 200 ° C. for 60 minutes.
<ピール強度の測定>
前記の方法で作製したサンプルを用いて、JIS C6481に従って測定し、下記の基準で評価した。
◎:0.5kN/m以上
○:0.5kN/m未満0.4kN/m以上
×:0.4kN/m未満
−:得られる硬化物が脆い為、強度不足により測定不可
<Measurement of peel strength>
Using the sample prepared by the above method, it was measured according to JIS C6481 and evaluated according to the following criteria.
⊚: 0.5 kN / m or more ○: less than 0.5 kN / m 0.4 kN / m or more ×: less than 0.4 kN / m −: Since the obtained cured product is brittle, measurement is not possible due to insufficient strength.
表中の成分の詳細は以下のとおりである。
jER(登録商標)630: 以下の化学構造式を主成分とするエポキシ樹脂(三菱ケミカル株式会社製)
NC−3000−H: ビフェニル骨格含有多官能固形エポキシ樹脂(日本化薬社製)
C−1: 合成例1により製造
C−2: 合成例2により製造
SO−C2: フェニルアミノシラン処理した球状シリカ(平均粒径:0.5μm、単位質量あたりのカーボン量0.18)(アドマテックス社製)
YX6954 BH30: フェノキシ樹脂 (三菱ケミカル社製)
IB2PZ: 1−ベンジル−2−フェニルイミダゾール
The details of the components in the table are as follows.
jER (registered trademark) 630: Epoxy resin containing the following chemical structural formula as the main component (manufactured by Mitsubishi Chemical Corporation)
NC-3000-H: Biphenyl skeleton-containing polyfunctional solid epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
C-1: Manufactured according to Synthesis Example 1 C-2: Manufactured according to Synthesis Example 2 SO-C2: Spherical silica treated with phenylaminosilane (average particle size: 0.5 μm, carbon content per unit mass 0.18) (Admatex Made by the company)
YX6954 BH30: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation)
IB2PZ: 1-benzyl-2-phenylimidazole
実施例の硬化性樹脂組成物は、高耐熱性と高密着性と低誘電正接とを兼ね備えていることがわかる。 It can be seen that the curable resin composition of the example has high heat resistance, high adhesion, and low dielectric loss tangent.
Claims (9)
(B)窒素原子を含まないエポキシ樹脂と、
(C)活性エステル基を有する化合物と、
(D)無機フィラーと、
を含有する硬化性樹脂組成物であって、
前記(A)窒素原子を含むエポキシ樹脂および前記(B)窒素原子を含まないエポキシ樹脂におけるエポキシ基の総量の、前記(C)活性エステル基を有する化合物におけるエステル基の総量に対する比が0.2〜0.6であり、
前記(A)窒素原子を含むエポキシ樹脂が、分子中に窒素原子を1個〜4個およびエポキシ基を3個以上有する3官能以上の多官能エポキシ樹脂であり、
前記(B)窒素原子を含まないエポキシ樹脂が、ビフェニルアラルキル型エポキシ樹脂であり、
前記(C)活性エステル基を有する化合物が、下記一般式(1)
前記(D)無機フィラーはシリカであり、
前記シリカの配合量は、硬化性樹脂組成物中の固形分を100質量%とした場合、65質量%以上であることを特徴とする硬化性樹脂組成物。 (A) Epoxy resin containing nitrogen atoms and
(B) Epoxy resin containing no nitrogen atom and
(C) A compound having an active ester group and
(D) Inorganic filler and
A curable resin composition containing
The ratio of the total amount of epoxy groups in the (A) epoxy resin containing a nitrogen atom and the (B) epoxy resin not containing a nitrogen atom to the total amount of ester groups in the compound having the (C) active ester group is 0.2. 0.6 der is,
The epoxy resin (A) containing a nitrogen atom is a trifunctional or higher functional epoxy resin having 1 to 4 nitrogen atoms and 3 or more epoxy groups in the molecule.
The epoxy resin (B) containing no nitrogen atom is a biphenyl aralkyl type epoxy resin.
The compound having the active ester group (C) has the following general formula (1).
The inorganic filler (D) is silica.
The amount of silica is curable if the solid content of the resin composition was 100% by mass, a curable resin composition, characterized in der Rukoto least 65 wt%.
(B)窒素原子を含まないエポキシ樹脂と、
(C)活性エステル基を有する化合物と、
(D)無機フィラーと、
を含有する硬化性樹脂組成物であって、
前記(A)窒素原子を含むエポキシ樹脂および前記(B)窒素原子を含まないエポキシ樹脂におけるエポキシ基の総量の、前記(C)活性エステル基を有する化合物におけるエステル基の総量に対する比が0.2〜0.6であり、
前記(A)窒素原子を含むエポキシ樹脂が、分子中に窒素原子を1個〜4個およびエポキシ基を3個以上有する3官能以上の多官能エポキシ樹脂であり、
前記(B)窒素原子を含まないエポキシ樹脂が、ビフェニルアラルキル型エポキシ樹脂であり、
前記(C)活性エステル基を有する化合物が、下記一般式(2):
mは1〜6の整数であり、nはそれぞれ独立的に1〜5の整数であり、qはそれぞれ独立的に1〜6の整数であり、
式(3)中、kはそれぞれ独立的に1〜5の整数であり、
式(4)中、Yは上記式(3)で表される基(kはそれぞれ独立的に1〜5の整数)であり、tはそれぞれ独立的に0〜5の整数である)
で表される構造部位を有し、その両末端が一価のアリールオキシ基である構造を有する化合物であり、
前記(D)無機フィラーはシリカであり、
前記シリカの配合量は、硬化性樹脂組成物中の固形分を100質量%とした場合、65質量%以上であることを特徴とする硬化性樹脂組成物。 (A) Epoxy resin containing nitrogen atoms and
(B) Epoxy resin containing no nitrogen atom and
(C) A compound having an active ester group and
(D) Inorganic filler and
A curable resin composition containing
The ratio of the total amount of epoxy groups in the (A) epoxy resin containing a nitrogen atom and the (B) epoxy resin not containing a nitrogen atom to the total amount of ester groups in the compound having the (C) active ester group is 0.2. ~ 0.6,
The epoxy resin (A) containing a nitrogen atom is a trifunctional or higher functional epoxy resin having 1 to 4 nitrogen atoms and 3 or more epoxy groups in the molecule.
The epoxy resin (B) containing no nitrogen atom is a biphenyl aralkyl type epoxy resin.
The compound having the active ester group (C) has the following general formula (2):
m is an integer of 1 to 6, n is an integer of 1 to 5 independently, and q is an integer of 1 to 6 independently.
In equation (3), k is an integer of 1 to 5 independently.
In the formula (4), Y is a group represented by the above formula (3) (k is an integer of 1 to 5 independently), and t is an integer of 0 to 5 independently).
Having a structural moiety represented in, Ri compound der whose both ends have a structure an aryloxy group monovalent,
The inorganic filler (D) is silica.
The amount of silica is curable if the solid content of the resin composition was 100% by mass, a curable resin composition, characterized in der Rukoto least 65 wt%.
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