JP2023075383A - Polyimide resin composition and cured body thereof - Google Patents
Polyimide resin composition and cured body thereof Download PDFInfo
- Publication number
- JP2023075383A JP2023075383A JP2021188252A JP2021188252A JP2023075383A JP 2023075383 A JP2023075383 A JP 2023075383A JP 2021188252 A JP2021188252 A JP 2021188252A JP 2021188252 A JP2021188252 A JP 2021188252A JP 2023075383 A JP2023075383 A JP 2023075383A
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- Prior art keywords
- resin
- copper foil
- group
- component
- compound
- 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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- 229920001721 polyimide Polymers 0.000 title claims abstract description 40
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title description 15
- 229920005989 resin Polymers 0.000 claims abstract description 191
- 239000011347 resin Substances 0.000 claims abstract description 191
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000011889 copper foil Substances 0.000 claims abstract description 102
- 239000011342 resin composition Substances 0.000 claims abstract description 82
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 11
- 230000003746 surface roughness Effects 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 64
- -1 aminophenol compound Chemical class 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 53
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 48
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 34
- 125000000524 functional group Chemical group 0.000 claims description 26
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 125000003277 amino group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229920005575 poly(amic acid) Polymers 0.000 claims description 11
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000005647 linker group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 238000004438 BET method Methods 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 58
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 42
- 230000015572 biosynthetic process Effects 0.000 description 34
- 238000003786 synthesis reaction Methods 0.000 description 34
- 238000001723 curing Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 22
- 150000004985 diamines Chemical class 0.000 description 20
- 239000003822 epoxy resin Substances 0.000 description 20
- 229920000647 polyepoxide Polymers 0.000 description 20
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 19
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000004593 Epoxy Substances 0.000 description 16
- 150000008065 acid anhydrides Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 150000003949 imides Chemical class 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 239000000539 dimer Substances 0.000 description 9
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 8
- 125000004018 acid anhydride group Chemical group 0.000 description 8
- 239000005350 fused silica glass Substances 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical class OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000006798 ring closing metathesis reaction Methods 0.000 description 7
- BCJIMAHNJOIWKQ-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-4-yl)oxy]-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2OC1=CC=CC2=C1C(=O)OC2=O BCJIMAHNJOIWKQ-UHFFFAOYSA-N 0.000 description 6
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 4
- 102100031503 Barrier-to-autointegration factor-like protein Human genes 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 101000729827 Homo sapiens Barrier-to-autointegration factor-like protein Proteins 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 3
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical class OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 2
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XINCECQTMHSORG-UHFFFAOYSA-N Isoamyl isovalerate Chemical compound CC(C)CCOC(=O)CC(C)C XINCECQTMHSORG-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FFOPEPMHKILNIT-UHFFFAOYSA-N Isopropyl butyrate Chemical compound CCCC(=O)OC(C)C FFOPEPMHKILNIT-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
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Landscapes
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Abstract
Description
本発明は、銅箔の表面に熱硬化性の樹脂組成物からなる樹脂層を有する樹脂付き銅箔、及び該樹脂付き銅箔の有する樹脂層を硬化させた銅張積層体に関する。 The present invention relates to a resin-coated copper foil having a resin layer made of a thermosetting resin composition on the surface of the copper foil, and a copper-clad laminate obtained by curing the resin layer of the resin-coated copper foil.
スマートフォンやタブレット等のモバイル通信機器や通信基地局装置、コンピュータやカーナビゲーション等の電子機器に不可欠な部材としてプリント配線板が挙げられる。プリント配線板には金属箔との密着性、耐熱性及び柔軟性等の特性に優れた各種の樹脂材料が用いられている。また、近年では高速で大容量の次世代高周波無線用のプリント配線板の開発が行われており、上記の諸特性に加え、樹脂材料には低伝送損失であること、即ち低誘電・低誘電正接であることが求められている。 BACKGROUND ART Printed wiring boards are indispensable members for electronic devices such as mobile communication devices such as smartphones and tablets, communication base station devices, computers and car navigation systems. 2. Description of the Related Art Various resin materials having excellent properties such as adhesion to metal foil, heat resistance and flexibility are used for printed wiring boards. In recent years, high-speed, large-capacity printed wiring boards for next-generation high-frequency radio have been developed. It is required to be tangent.
通信機器や電子機器等には、大容量の情報を高速で伝送・処理することを目的として高周波の電気信号が使用されているが、高周波信号は非常に減衰しやすいため、プリント配線板にも伝送損失を低減する工夫が求められる。伝送損失は導体損失と誘電体損失に大別されるが、電気信号の周波数がGHzを超えると、導体損失は回路に使用される銅箔の表面状態に依存するため、導体損失を抑えるためには一般的には低粗度または無粗化の銅箔を用いることが好ましく、即ち、これらの銅箔に対する高い接着性を有する低誘電樹脂が求められている。 High-frequency electrical signals are used in communication equipment and electronic equipment for the purpose of transmitting and processing large amounts of information at high speed. A device to reduce the transmission loss is required. Transmission loss is roughly divided into conductor loss and dielectric loss. When the frequency of the electrical signal exceeds GHz, conductor loss depends on the surface condition of the copper foil used in the circuit. In general, it is preferable to use low-roughness or non-roughened copper foils, ie, low dielectric resins with high adhesion to these copper foils are desired.
耐熱性、難燃性、柔軟性、電気特性及び耐薬品性等の特性に優れたポリイミド樹脂は、電気・電子部品、半導体、通信機器及びその回路部品、周辺機器等に広く使用されている。特に構造の工夫等により溶剤溶解性を向上させた可溶性ポリイミド樹脂は、加工や塗工が容易であり、しかもその使用時には高温を要するイミド化工程が不要なため、広い範囲で使用されている。
その一方で、石油や天然油等の炭化水素系化合物が高い絶縁性と低い誘電率を示すことが知られている。
Polyimide resins, which are excellent in properties such as heat resistance, flame retardancy, flexibility, electrical properties, and chemical resistance, are widely used in electrical and electronic parts, semiconductors, communication equipment and its circuit parts, peripheral equipment, and the like. In particular, soluble polyimide resins, whose solvent solubility has been improved by structural devising, etc., are easy to process and coat, and are used in a wide range because they do not require imidization processes that require high temperatures when used.
On the other hand, it is known that hydrocarbon compounds such as petroleum and natural oils exhibit high insulating properties and low dielectric constants.
特許文献1及び2には、長鎖アルキル鎖を有するダイマージアミンの骨格を導入したポリイミド樹脂を含有する樹脂組成物及びこれを用いた樹脂付き銅箔が記載されており、これらの樹脂組成物は銅箔に対する接着性と高いはんだ耐熱性を有している。
しかしながら、高周波領域においては更なる伝送損失の低減が求められるため、エポキシ樹脂のような誘電特性を悪化させる成分を減らす必要がある。また、銅箔表面の粗度が大きくなると高周波領域における伝送損失が増大することが知られているため、伝送損失を低減するためには銅箔の粗度を小さくする必要があるが、銅箔の粗度が小さくなると樹脂組成物の銅箔に対する接着性が低下してしまう。
Patent Documents 1 and 2 describe a resin composition containing a polyimide resin into which a dimer diamine skeleton having a long alkyl chain is introduced and a resin-coated copper foil using the same, and these resin compositions are Adhesion to copper foil and high solder heat resistance.
However, since further reduction in transmission loss is required in the high frequency region, it is necessary to reduce components such as epoxy resin that deteriorate dielectric properties. In addition, it is known that the transmission loss in the high-frequency region increases when the surface roughness of the copper foil increases. If the roughness of the resin composition becomes small, the adhesiveness of the resin composition to the copper foil is lowered.
特許文献3には、誘電特性を向上させるため、ダイマージアミンの骨格を導入したポリイミド樹脂にシリカを添加する例が記載されている。しかしながら、特許文献3に記載の樹脂組成物はエポキシ樹脂の含有割合が高く、誘電特性低減効果が不充分なことに加え、フィラーの添加量が多いため銅箔に対する塗工性が悪いという問題があった。 Patent Document 3 describes an example in which silica is added to a polyimide resin into which a dimer diamine skeleton has been introduced in order to improve dielectric properties. However, the resin composition described in Patent Document 3 has a high epoxy resin content, and in addition to an insufficient effect of reducing dielectric properties, there is a problem that the amount of filler added is poor, so that the coating properties on copper foil are poor. there were.
上記問題に対して、特許文献4には、樹脂組成物中のエポキシ樹脂の含有割合を低減することで高い誘電特性を実現したことが記載されている。しかしながら、特許文献4の組成物は熱硬化樹脂の含有割合が低いため、硬化物の架橋密度が低く、耐熱性が低いという問題があった。 In response to the above problem, Patent Document 4 describes that high dielectric properties are achieved by reducing the content of epoxy resin in the resin composition. However, since the composition of Patent Document 4 contains a low thermosetting resin content, the cured product has a low crosslink density and low heat resistance.
本発明の目的は、塗工性に優れた樹脂組成物からなる樹脂層を有する樹脂付き銅箔、及び該樹脂付き銅箔の有する樹脂組成物からなる樹脂層を硬化させて得られる銅張積層体であって、樹脂層の硬化物と銅箔との接着性に優れ、樹脂層の硬化物の耐熱性が良好であると共に、誘電特性に優れる銅張積層体を提供することにある。 An object of the present invention is to provide a resin-coated copper foil having a resin layer made of a resin composition having excellent coatability, and a copper clad laminate obtained by curing the resin layer made of the resin composition of the resin-coated copper foil. To provide a copper-clad laminate which is a body, has excellent adhesiveness between a cured product of a resin layer and a copper foil, has good heat resistance of the cured product of the resin layer, and has excellent dielectric properties.
本発明者らは鋭意検討を行った結果、低粗度銅箔の粗化面又は無粗化銅箔の表面に、特定構造の変性ポリイミド樹脂、特定の比表面積を有するシリカ、熱硬化性樹脂及び硬化剤を含有する樹脂組成物からなる樹脂層を有する樹脂付き銅箔が上記の課題を解決することを見出し、本発明を完成させた。
即ち本発明は、
(1)表面粗さ(Rz)が1.1μm以下の銅箔の粗化面又は無粗化銅箔の表面に樹脂組成物からなる樹脂層を有する樹脂付き銅箔であって、該樹脂組成物が、一分子中に少なくとも二個のアミノ基を有するアミノフェノール化合物(a1)、炭素数6乃至36の脂肪族ジアミノ化合物(a2)及びフェノール性水酸基を有さない芳香族ジアミノ化合物(a3)を含むアミノ化合物(A)と四塩基酸二無水物(B)との共重合物であるポリアミック酸樹脂のイミド化物(P)と、フェノール性水酸基と反応し得る官能基とエチレン性不飽和二重結合基を有する化合物(C)との反応物であるポリイミド樹脂(D)、BET法における比表面積が、1.0乃至20m2/gであるシリカ(E)、熱硬化性樹脂(F)及び硬化剤(G)を含有する樹脂付き銅箔、
(2)シリカ(E)の含有量が、ポリイミド樹脂(D)の固形分に対して5乃至50質量%である前項(1)に記載の樹脂付き銅箔、
(3)シリカ(E)の平均粒子径が、0.3乃至5.0μmである前項(1)又は(2)に記載の樹脂付き銅箔、
(4)シリカ(E)が、シラン化合物で表面処理を施されていないシリカである前項(1)乃至(3)のいずれか一項に記載の樹脂付き銅箔、
(5)一分子中に少なくとも二個のアミノ基を有するアミノフェノール化合物(a1)が、下記式(1)
As a result of extensive studies, the present inventors found that a modified polyimide resin with a specific structure, silica having a specific specific surface area, a thermosetting resin The inventors have found that a resin-coated copper foil having a resin layer made of a resin composition containing a curing agent and a curing agent can solve the above problems, and completed the present invention.
That is, the present invention
(1) A resin-coated copper foil having a resin layer made of a resin composition on the roughened surface of the copper foil or the surface of the non-roughened copper foil having a surface roughness (Rz) of 1.1 μm or less, wherein the resin composition The substance is an aminophenol compound (a1) having at least two amino groups in one molecule, an aliphatic diamino compound (a2) having 6 to 36 carbon atoms, and an aromatic diamino compound (a3) having no phenolic hydroxyl group An imidized product (P) of a polyamic acid resin which is a copolymer of an amino compound (A) and a tetrabasic dianhydride (B) containing a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated di Polyimide resin (D) which is a reaction product with compound (C) having a heavy bond group, silica (E) having a specific surface area determined by BET method of 1.0 to 20 m 2 /g, thermosetting resin (F) and a resin-coated copper foil containing a curing agent (G),
(2) The resin-coated copper foil according to (1) above, wherein the content of silica (E) is 5 to 50% by mass with respect to the solid content of the polyimide resin (D);
(3) The resin-coated copper foil according to (1) or (2) above, wherein the silica (E) has an average particle size of 0.3 to 5.0 μm;
(4) The resin-coated copper foil according to any one of (1) to (3) above, wherein the silica (E) is silica not surface-treated with a silane compound;
(5) an aminophenol compound (a1) having at least two amino groups in one molecule, represented by the following formula (1)
(式(1)中、R1は水素原子、メチル基又はエチル基を表し、XはC(CH3)2、C(CF3)2、SO2、酸素原子、直接結合又は下記式(2) (In formula (1), R 1 represents a hydrogen atom, a methyl group or an ethyl group, X is C(CH 3 ) 2 , C(CF 3 ) 2 , SO 2 , an oxygen atom, a direct bond or the following formula (2) )
で表される二価の連結基を表す。)
で表される化合物を含む前項(1)に記載の樹脂付き銅箔、
(6)四塩基酸二無水物(B)が、下記式(3)乃至(11)
Represents a divalent linking group represented by )
The resin-coated copper foil according to the preceding item (1) containing a compound represented by
(6) Tetrabasic dianhydride (B) is represented by the following formulas (3) to (11)
(式(6)中、YはC(CF3)2、SO2、CO、酸素原子、直接結合又は下記式(2) (In formula (6), Y is C(CF 3 ) 2 , SO 2 , CO, an oxygen atom, a direct bond, or the following formula (2)
で表される二価の連結基を表す。)
からなる群より選択される化合物を含む前項(1)に記載の樹脂付き銅箔、
(7)フェノール性水酸基と反応し得る官能基とエチレン性不飽和二重結合基を有する化合物(C)が有するフェノール性水酸基と反応しうる官能基が、イソシアネート基又はカルボン酸クロリド基である前項(1)に記載の樹脂付き銅箔、
(8)フェノール性水酸基を有さない芳香族ジアミノ化合物(a3)が、下記式(12)乃至(15)
Represents a divalent linking group represented by )
The resin-coated copper foil according to the preceding item (1) containing a compound selected from the group consisting of
(7) The functional group capable of reacting with the phenolic hydroxyl group in the compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is an isocyanate group or a carboxylic acid chloride group. The resin-coated copper foil according to (1),
(8) The aromatic diamino compound (a3) having no phenolic hydroxyl group is represented by the following formulas (12) to (15)
(式(14)中、R2は独立してメチル基又はトリフルオロメチル基を表し、式(15)中、ZはCH(CH3)、SO2、CH2、O-C6H4-O、酸素原子、直接結合又は下記式(2) (In formula (14), R 2 independently represents a methyl group or a trifluoromethyl group; in formula (15), Z is CH(CH 3 ), SO 2 , CH 2 , O—C 6 H 4 — O, an oxygen atom, a direct bond, or the following formula (2)
で表される二価の連結基を、R3は独立して水素原子、メチル基、エチル基又はトリフルオロメチル基を表す。)からなる群より選択される化合物を含む前項(1)に記載の樹脂付き銅箔、
(9)熱硬化性樹脂(F)が、芳香族マレイミド樹脂を含有する前項(1)に記載の樹脂付き銅箔、及び
(10)前項(1)乃至(9)のいずれか一項に記載の樹脂付き銅箔の有する樹脂組成物からなる樹脂層を硬化させて得られる銅張積層体、
に関する。
R3 independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group. ) The resin-coated copper foil according to the preceding item (1) containing a compound selected from the group consisting of
(9) The resin-coated copper foil according to the preceding item (1), wherein the thermosetting resin (F) contains an aromatic maleimide resin, and (10) The resin-coated copper foil according to any one of the preceding items (1) to (9). A copper-clad laminate obtained by curing a resin layer made of a resin composition possessed by the resin-coated copper foil of
Regarding.
本発明の樹脂付き銅箔の有する樹脂層となる樹脂組成物は塗工性に優れるため、容易な方法で樹脂付き銅箔を調製することが出来る。また、本発明の樹脂付き銅箔の有する樹脂組成物からなる樹脂層を硬化させて得られる銅張積層体は、樹脂層の硬化物と銅箔との接着性に優れ、樹脂層の硬化物の耐熱性が良好であると共に、誘電特性に優れるため、プリント配線板等に好適に用いることができる。 Since the resin composition that forms the resin layer of the resin-coated copper foil of the present invention has excellent coatability, the resin-coated copper foil can be prepared by a simple method. In addition, the copper-clad laminate obtained by curing the resin layer made of the resin composition of the resin-coated copper foil of the present invention has excellent adhesion between the cured resin layer and the copper foil, and the cured resin layer has excellent adhesion. It has good heat resistance and excellent dielectric properties, so it can be suitably used for printed wiring boards and the like.
以下に本発明を詳細に説明する。
本発明の樹脂付き銅箔は、
(1)表面粗さ(Rz)が1.1μm以下の銅箔の粗化面又は無粗化銅箔の表面に樹脂組成物からなる樹脂層を有する樹脂付き銅箔であって、該樹脂組成物が、一分子中に少なくとも二個のアミノ基を有するアミノフェノール化合物(a1)(以下、単に「(a1)成分」とも記載する)、炭素数6乃至36の脂肪族ジアミノ化合物(a2)(以下、単に「(a2)成分」とも記載する)及びフェノール性水酸基を有さない芳香族ジアミノ化合物(a3)(以下、単に「(a3)成分」とも記載する)を含むアミノ化合物(A)(以下、単に「(A)成分」とも記載する)と四塩基酸二無水物(B)(以下、単に「(B)成分」とも記載する)との共重合物であるポリアミック酸樹脂のイミド化物(P)(以下、単に「イミド化物(P)」とも記載する)と、フェノール性水酸基と反応し得る官能基とエチレン性不飽和二重結合基を有する化合物(C)(以下、単に「(C)成分」とも記載する)との反応物であるポリイミド樹脂(D)(以下、単に「(D)成分」とも記載する)、BET法における比表面積が、1.0乃至20m2/gであるシリカ(E)(以下、単に「(E)成分」とも記載する)、熱硬化性樹脂(F)(以下、単に「(F)成分」とも記載する)及び硬化剤(G)(以下、単に「(G)成分」とも記載する)を含有する樹脂組成物(以下単に「樹脂組成物」とも記載する)からなる樹脂層を有する。
先ず、(D)成分の中間原料であるイミド化物(P)について説明する。
The present invention will be described in detail below.
The resin-coated copper foil of the present invention is
(1) A resin-coated copper foil having a resin layer made of a resin composition on the roughened surface of the copper foil or the surface of the non-roughened copper foil having a surface roughness (Rz) of 1.1 μm or less, wherein the resin composition The substance is an aminophenol compound (a1) having at least two amino groups in one molecule (hereinafter also simply referred to as "component (a1)"), an aliphatic diamino compound having 6 to 36 carbon atoms (a2) ( hereinafter simply referred to as "(a2) component") and an amino compound (A) containing an aromatic diamino compound (a3) having no phenolic hydroxyl group (hereinafter also simply referred to as "(a3) component") Hereinafter, simply referred to as "component (A)") and tetrabasic dianhydride (B) (hereinafter also simply referred to as "component (B)"), which is an imidized polyamic acid resin. (P) (hereinafter also simply referred to as “imidated product (P)”) and a compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group (hereinafter simply referred to as “( Polyimide resin (D) (hereinafter also simply referred to as "(D) component"), which is a reaction product with (also referred to as "component C)", has a specific surface area in the BET method of 1.0 to 20 m 2 /g A certain silica (E) (hereinafter simply referred to as "(E) component"), a thermosetting resin (F) (hereinafter simply referred to as "(F) component") and a curing agent (G) (hereinafter simply referred to as "(F) component") It has a resin layer made of a resin composition (hereinafter also simply referred to as "resin composition") containing (also simply referred to as "component (G)").
First, the imidized product (P), which is an intermediate raw material for the component (D), will be described.
イミド化物(P)の合成に用いられる(a1)成分は、一分子中に少なくとも二個のアミノ基と少なくとも一個のフェノール性水酸基を有する化合物であれば特に限定されない。(a1)成分の具体例としては、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルスルホン、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルエーテル、3,3’-ジアミノ-4,4’-ジヒドロキシビフェニル、3,3’-ジアミノ-4,4’-ジヒドロキシベンゾフェノン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)メタン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)エタン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、1,3-ヘキサフルオロ-2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン及び9,9’-ビス(3-アミノ-4-ヒドロキシフェニル)フルオレン等が挙げられる。これらは1種を用いてもよく、2種以上を混合して用いてもよい。 The component (a1) used for synthesizing the imidized compound (P) is not particularly limited as long as it is a compound having at least two amino groups and at least one phenolic hydroxyl group in one molecule. Specific examples of component (a1) include 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′-diamino-4, 4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4- hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane and 9,9' -Bis(3-amino-4-hydroxyphenyl)fluorene and the like. These may be used alone or in combination of two or more.
イミド化物(P)の合成に用いられる(a1)成分は、下記式(1)で示される化合物を含有することが好ましい。 The component (a1) used for synthesizing the imidized compound (P) preferably contains a compound represented by the following formula (1).
(式(1)中、R1は水素原子、メチル基又はエチル基を表し、XはC(CH3)2、C(CF3)2、SO2、酸素原子、直接結合又は下記式(2)で表される二価の連結基を表す。 (In formula (1), R 1 represents a hydrogen atom, a methyl group or an ethyl group, X is C(CH 3 ) 2 , C(CF 3 ) 2 , SO 2 , an oxygen atom, a direct bond or the following formula (2) ) represents a divalent linking group.
イミド化物(P)を合成する際の(a1)成分の使用量は、イミド化物(P)のフェノール性水酸基当量が1,500乃至25,000g/eq.の範囲となる量が好ましい。フェノール性水酸基当量が1,500g/eq.を下回る場合は、最終的に得られる(D)成分の極性が高くなるため樹脂組成物の硬化物の誘電正接が高くなってしまい、25,000g/eq.を上回る場合は、後述する(C)成分との反応点が少なくなることによって最終的に得られる(D)成分の架橋点が少なくなり、樹脂組成物の硬化物の耐熱性や基材との接着性が低下する傾向にある。
尚、本明細書におけるフェノール性水酸基当量はJIS K-0070に準じた方法で測定した値を意味する。
The amount of component (a1) used when synthesizing the imidized product (P) is such that the phenolic hydroxyl equivalent of the imidized product (P) is 1,500 to 25,000 g/eq. is preferred. A phenolic hydroxyl equivalent of 1,500 g/eq. is lower than 25,000 g/eq. If it exceeds, the number of cross-linking points of the finally obtained component (D) decreases due to the decrease in the reaction points with the component (C) described later, and the heat resistance of the cured product of the resin composition and the compatibility with the substrate. Adhesion tends to decrease.
Incidentally, the phenolic hydroxyl group equivalent in the present specification means a value measured by a method according to JIS K-0070.
イミド化物(P)は、(A)成分と(B)成分の共重合物であるポリアミック酸樹脂のイミド化反応、即ち、脱水縮合による環化反応によって得られる。よって、意図した水酸基当量及び脂肪族鎖量を有するイミド化物(P)を合成するために必要な(A)成分および(B)成分の量(割合)は、共重合反応に用いる(A)成分および(B)成分それぞれの分子量と(a1)成分中のフェノール性水酸基の数から容易に算出することができる。 The imidized product (P) is obtained by an imidization reaction of a polyamic acid resin which is a copolymer of the components (A) and (B), ie, a cyclization reaction by dehydration condensation. Therefore, the amounts (ratios) of the components (A) and (B) necessary for synthesizing the imidized product (P) having the intended hydroxyl group equivalent and aliphatic chain content are and (B) components and the number of phenolic hydroxyl groups in component (a1).
イミド化物(P)の合成に用いられる(a2)成分は、一分子中に二個のアミノ基を有する炭素数6乃至36の脂肪族化合物であれば特に限定されない。(a2)成分中の脂肪族構造は直鎖、分岐鎖又は環状の何れであってもよく、前記の構造を併せ持つものでもよく、また、飽和の脂肪族及び不飽和の脂肪族の何れであってもよい。
(a2)成分の具体例としては、ヘキサメチレンジアミン、1,3-ビス(アミノメチル)シクロヘキサン、1,3-ビスアミノメチルシクロヘキサン、ノルボルナンジアミン、イソホロンジアミン、ダイマージアミン、2-メチル-1,5-ジアミノペンタン、1,7-ジアミノヘプタン、1,8-ジアミノオクタン、1,9-ジアミノノナン、1,10-ジアミノデカン、1,11-ジアミノウンデカン、1,12-ジアミノドデカン、1,4-ビス(アミノメチル)シクロヘキサン、4,4’-メチレンビスシクロヘキシルアミン及び炭素数6乃至36のジアミノポリシロキサン等が挙げられる。これらは1種を用いてもよく、2種以上を混合して用いてもよい。また、最終的に得られる(D)成分の誘電特性の観点から、ダイマージアミンを用いることが好ましい。
The component (a2) used in the synthesis of the imidized product (P) is not particularly limited as long as it is an aliphatic compound having 6 to 36 carbon atoms and having two amino groups in one molecule. The aliphatic structure in the component (a2) may be linear, branched or cyclic, or may have the above structures, and may be saturated or unsaturated. may
Specific examples of component (a2) include hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,3-bisaminomethylcyclohexane, norbornanediamine, isophoronediamine, dimerdiamine, 2-methyl-1,5 -diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,4-bis (Aminomethyl)cyclohexane, 4,4′-methylenebiscyclohexylamine, diaminopolysiloxane having 6 to 36 carbon atoms, and the like. These may be used alone or in combination of two or more. From the viewpoint of the dielectric properties of the finally obtained component (D), dimer diamine is preferably used.
(a2)成分の具体例の項に記載したダイマージアミンとは、オレイン酸等の不飽和脂肪酸の二量体であるダイマー酸の有する二つのカルボキシル基を一級アミノ基に置換したものである(特開平9-12712号公報等参照)。ダイマージアミンの市販品の具体例としては、PRIAMINE1074並びにPRIAMINE1075(いずれもクローダジャパン株式会社製)、及びバーサミン551(コグニスジャパン株式会社製)等が挙げられる。これらは1種を用いてもよく、2種以上を混合して用いてもよい。以下、ダイマージアミンの非限定的な一般式を示す(各式において、m+n=6乃至17が好ましく、p+q=8乃至19が好ましく、破線部は炭素-炭素単結合又は炭素-炭素二重結合を意味する)。 The dimer diamine described in the specific examples of component (a2) is obtained by substituting primary amino groups for the two carboxyl groups of dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid. See Japanese Laid-Open Patent Publication No. 9-12712, etc.). Specific examples of commercially available dimer diamines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.) and Versamin 551 (manufactured by Cognis Japan Co., Ltd.). These may be used alone or in combination of two or more. Hereinafter, non-limiting general formulas of dimer diamines are shown (in each formula, m + n = 6 to 17 is preferable, p + q = 8 to 19 is preferable, and the broken line indicates a carbon-carbon single bond or a carbon-carbon double bond. means).
イミド化物(P)を合成する際の(a2)成分の使用量は、(A)成分の質量から、(B)成分のモル数の2倍のモル数の水(脱水縮合反応によって生成した水)の質量を除した質量(生成したイミド化物(P)の質量)の10乃至50質量%の範囲となる量が好ましい。(a2)成分の量が前記の範囲を下回ると、最終的に得られる(D)成分中の(a2)成分に由来する脂肪族鎖が少な過ぎて樹脂組成物の硬化物の誘電正接が高くなってしまい、前記の範囲を上回ると、(D)成分中の(a2)成分に由来する脂肪族鎖が多過ぎて樹脂組成物の硬化物の耐熱性が低下する。 The amount of component (a2) used when synthesizing the imidized product (P) is determined by dividing the mass of component (A) by the number of moles of water (water generated by the dehydration condensation reaction) that is twice the number of moles of component (B). ) (the mass of the imidized product (P) produced) is preferably in the range of 10 to 50% by mass. If the amount of component (a2) is less than the above range, the number of aliphatic chains derived from component (a2) in component (D) finally obtained is too small, and the dielectric loss tangent of the cured product of the resin composition is high. When the above range is exceeded, the number of aliphatic chains derived from component (a2) in component (D) is too large, and the heat resistance of the cured product of the resin composition is lowered.
イミド化物(P)の合成に用いられる(a3)成分は、前記の(a1)成分以外の芳香族ジアミノ化合物であって、一分子中に二個のアミノ基を有する芳香族系の化合物であれば特に限定されない。(a3)成分の具体例としては、m-フェニレンジアミン、p-フェニレンジアミン、m-トリレンジアミン、4,4’-ジアミノジフェニルエーテル、3,3’-ジメチル-4,4’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルチオエーテル、3,3’-ジメチル-4,4’-ジアミノジフェニルチオエーテル、3,3’-ジエトキシ-4,4’-ジアミノジフェニルチオエーテル、3,3’-ジアミノジフェニルチオエーテル、4,4’-ジアミノベンゾフェノン、3,3’-ジメチル-4,4’-ジアミノベンゾフェノン、3,3’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、3,3’-ジメトキシ-4,4’-ジアミノジフェニルチオエーテル、2,2’-ビス(3-ミノフェニル)プロパン、2,2’-ビス(4-アミノフェニル)プロパン、4,4’-ジアミノジフェニルスルフォキサイド、3,3’-ジアミノジフェニルスルフォンスルホン、4,4’-ジアミノジフェニルスルフォンスルホン、ベンチジン、3,3’-ジメチルベンチジン、3,3’-ジメトキシベンチジン、3,3’-ジアミノビフェニル、p-キシリレンジアミン、m-キシリレンジアミン、o-キシリレンジアミン、2,2’-ビス(3-アミノフェノキシフェニル)プロパン、2,2’-ビス(4-アミノフェノキシフェニル)プロパン、1,3-ビス(4-アミノフェノキシフェニル)ベンゼン、1,3’-ビス(3-アミノフェノキシフェニル)プロパン、ビス(4-アミノ-3-メチルフェニル)メタン、ビス(4-アミノ-3,5-ジメチルフェニル)メタン、ビス(4-アミノ-3-エチルフェニル)メタン、ビス(4-アミノ-3,5-ジエチルフェニル)メタン、ビス(4-アミノ-3-プロピルフェニル)メタン及びビス(4-アミノ-3,5-ジプロピルフェニル)メタン等が挙げられる。これらは1種を用いてもよく、2種以上を混合して用いてもよい。 The component (a3) used in the synthesis of the imidized product (P) may be an aromatic diamino compound other than the component (a1), and may be an aromatic compound having two amino groups in one molecule. is not particularly limited. Specific examples of component (a3) include m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 3, 3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenylthioether, 2,2′-bis(3-aminophenyl)propane, 2,2′-bis(4-aminophenyl)propane, 4,4 '-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3 , 3′-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2′-bis(3-aminophenoxyphenyl)propane, 2,2′-bis(4-amino phenoxyphenyl)propane, 1,3-bis(4-aminophenoxyphenyl)benzene, 1,3′-bis(3-aminophenoxyphenyl)propane, bis(4-amino-3-methylphenyl)methane, bis(4 -amino-3,5-dimethylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-propylphenyl) ) methane and bis(4-amino-3,5-dipropylphenyl)methane. These may be used alone or in combination of two or more.
イミド化物(P)の合成に用いられる(a3)成分は、樹脂組成物の硬化物の耐熱性と最終的に得られる(D)成分の溶剤への溶解性の観点から、下記式(12)乃至(15)からなる群より選択される化合物を含有することが好ましい。 The (a3) component used for the synthesis of the imidized product (P) is the following formula (12) from the viewpoint of the heat resistance of the cured product of the resin composition and the solubility of the finally obtained component (D) in a solvent. It preferably contains a compound selected from the group consisting of (15).
式(14)中、R2は独立してメチル基又はトリフルオロメチル基を表す。式(15)中、R3は独立して水素原子、メチル基又はエチル基を、ZはCH(CH3)、SO2、CH2、O-C6H4-O、酸素原子、直接結合又は上記式(2)で表される二価の連結基を表す。 In formula (14), R2 independently represents a methyl group or a trifluoromethyl group. In formula (15), R 3 is independently a hydrogen atom, a methyl group or an ethyl group; Z is CH(CH 3 ), SO 2 , CH 2 , O—C 6 H 4 —O, an oxygen atom, or a direct bond; Or represents a divalent linking group represented by the above formula (2).
イミド化物(P)の合成に用いられる(B)成分は、一分子中に二個の酸無水物基を有するものであれば特に限定されない。
(B)成分の具体例としては、無水ピロメリット酸、エチレングリコール-ビス(アンヒドロトリメリテート)、グリセリン-ビス(アンヒドロトリメリテート)モノアセテート、1,2,3,4,-ブタンテトラカルボン酸二無水物、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物、5-(2,5-ジオキソテトラヒドロ-3-フラニル)-3-メチルシクロヘキセン-1,2-ジカルボン酸無水物、3a,4,5,9b-テトラヒドロ-5-(テトラヒドロ-2,5-ジオキソ-3-フラニル)-ナフト[1,2-c]フラン-1,3-ジオン、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物、ビシクロ(2,2,2)-オクト-7-エン-2,3,5,6-テトラカルボン酸二無水物及びビシクロ[2.2.2]オクタン-2,3,5,6-テトラカルボン酸二無水物、5,5’-((プロパン-2,2-ジイルビス(4,1-フェニレン))ビス(オキシ))ビス(イソベンゾフラン-1,3-ジオン)等が挙げられる。なかでも、溶剤溶解性、基材への密着性の面から、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物又は3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物が好ましい。これらは1種を用いてもよく、2種以上を混合して用いてもよい。
The component (B) used for synthesis of the imidized compound (P) is not particularly limited as long as it has two acid anhydride groups in one molecule.
Specific examples of component (B) include pyromellitic anhydride, ethylene glycol-bis(anhydrotrimellitate), glycerin-bis(anhydrotrimellitate) monoacetate, 1,2,3,4,-butane Tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4 ,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methylcyclohexene -1,2-dicarboxylic anhydride, 3a,4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3- dione, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bicyclo[ 2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, 5,5′-((propane-2,2-diylbis(4,1-phenylene))bis(oxy)) bis(isobenzofuran-1,3-dione) and the like. Among them, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride and 3,3′,4,4′-benzophenonetetracarboxylic acid are preferred in terms of solvent solubility and adhesion to substrates. The dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride or 3,3′,4,4′-diphenylethertetracarboxylic dianhydride is preferred. These may be used alone or in combination of two or more.
イミド化物(P)の合成に用いられる(B)成分は、ポリアミック酸樹脂、イミド化物(P)および(D)成分の溶剤溶解性の観点から、下記式(3)乃至(11)からなる群より選択される化合物を含有することが好ましい。 The (B) component used in the synthesis of the imidized product (P) is a group consisting of the following formulas (3) to (11) from the viewpoint of the solvent solubility of the polyamic acid resin, the imidized product (P) and the (D) component. It is preferable to contain more selected compounds.
式(6)中、YはC(CF3)2、SO2、CO、酸素原子、直接結合又は上記式(2)で表される二価の連結基を表す。 In formula (6), Y represents C(CF 3 ) 2 , SO 2 , CO, an oxygen atom, a direct bond, or a divalent linking group represented by formula (2) above.
イミド化物(P)の合成に用いられる(A)成分中の(a1)成分のモル数をa1M、(a2)成分のモル数をa2M、(a3)成分のモル数をa3Mとした場合、a1M/(a1M+a2M+a3M)の値が0.01を超えて0.3未満であることが好ましく、0.03を超えて0.15未満であることがより好ましい。a1M/(a1M+a2M+a3M)が0.01以下の場合は、後述する(C)成分のとの反応部位が少なくなるため樹脂組成物の硬化物の基材接着性およびはんだ耐熱性が低下する傾向にある。また、a1M/(a1M+a2M+a3M)が0.3以上である場合は、樹脂組成物の硬化物の誘電特性が低下する傾向にある。 When the number of moles of component (a1) in component (A) used for synthesis of imidized compound (P) is a1M, the number of moles of component (a2) is a2M, and the number of moles of component (a3) is a3M, a1M The value of /(a1M+a2M+a3M) is preferably greater than 0.01 and less than 0.3, more preferably greater than 0.03 and less than 0.15. When a1M/(a1M+a2M+a3M) is 0.01 or less, the number of reaction sites with component (C), which will be described later, is reduced, so that the substrate adhesiveness and soldering heat resistance of the cured product of the resin composition tend to decrease. . Further, when a1M/(a1M+a2M+a3M) is 0.3 or more, the dielectric properties of the cured product of the resin composition tend to deteriorate.
また、a2M/(a1M+a2M+a3M)の値が0.2を超えて0.9未満であることが好ましく、0.3を超えて0.6未満であることがより好ましい。a2M/(a1M+a2M+a3M)が0.2以下の場合は、樹脂組成物の硬化物の誘電特性が悪化したり、(D)成分の溶剤溶解性が悪くなる傾向にある。また、a2M/(a1M+a2M+a3M)が0.9以上の場合は、樹脂組成物の硬化物の耐熱性が悪化する傾向にある。 Also, the value of a2M/(a1M+a2M+a3M) is preferably more than 0.2 and less than 0.9, more preferably more than 0.3 and less than 0.6. If a2M/(a1M+a2M+a3M) is less than 0.2, the dielectric properties of the cured product of the resin composition tend to deteriorate, and the solvent solubility of component (D) tends to deteriorate. Further, when a2M/(a1M+a2M+a3M) is 0.9 or more, the heat resistance of the cured product of the resin composition tends to deteriorate.
また、a3M/(a1M+a2M+a3M)の値が0.1を超えて0.8未満であることが好ましく、0.2を超えて0.6未満であることがより好ましい。a3M/(a1M+a2M+a3M)が0.1以下の場合は、樹脂組成物の硬化物のはんだ耐熱性が悪化する傾向にある。また、a3M/(a1M+a2M+a3M)が0.8以上の場合は、(D)成分の溶剤溶解性が悪化する傾向にある。 Also, the value of a3M/(a1M+a2M+a3M) is preferably more than 0.1 and less than 0.8, more preferably more than 0.2 and less than 0.6. When a3M/(a1M+a2M+a3M) is 0.1 or less, the soldering heat resistance of the cured product of the resin composition tends to deteriorate. Further, when a3M/(a1M+a2M+a3M) is 0.8 or more, the solvent solubility of component (D) tends to deteriorate.
(A)成分のモル数をMA、(B)成分のモル数をMBとし、MA/MB>1の関係を満たす量の(A)成分と(B)成分を共重合させると両末端がアミノ基のポリアミック酸樹脂のイミド化物(P)が得られる。このとき、MA/MBの値が1.0を越えて2.0未満の範囲であることが好ましく、1.0を越えて1.5未満以下の範囲であることがより好ましい。前記の値が2.0以上の場合には、(D)成分の高分子量化が不充分となるのに加え、未反応原料の残存率が高くなり、樹脂組成物の硬化後の耐熱性等の諸特性が低下する可能性がある。 The number of moles of component (A) is MA, and the number of moles of component (B) is MB. An imidized product (P) of the polyamic acid resin of the group is obtained. At this time, the value of MA/MB is preferably in the range of more than 1.0 and less than 2.0, more preferably more than 1.0 and less than 1.5. If the above value is 2.0 or more, in addition to insufficient increase in the molecular weight of the component (D), the residual rate of unreacted raw materials increases, and heat resistance after curing of the resin composition, etc. properties may be degraded.
(A)成分のモル数をMA、(B)成分のモル数をMBとし、MB/MA>1の関係を満たす量の(A)成分と(B)成分を共重合させると両末端がカルボン酸無水物基のポリアミック酸樹脂のイミド化物(P)が得られる。この時、MB/MAの値が1.0を越えて2.0未満の範囲であることが好ましく、1.0を越えて1.5未満以下の範囲であることがより好ましい。前記の値が2.0以上の場合には、(D)成分の高分子量化が不充分となるのに加え、未反応原料の残存率が高くなり、樹脂組成物の硬化後の耐熱性等の諸特性が低下する可能性がある。 The number of moles of component (A) is MA, and the number of moles of component (B) is MB. An imidized product (P) of a polyamic acid resin having an acid anhydride group is obtained. At this time, the value of MB/MA is preferably in the range of more than 1.0 and less than 2.0, more preferably more than 1.0 and less than 1.5. If the above value is 2.0 or more, in addition to insufficient increase in the molecular weight of the component (D), the residual rate of unreacted raw materials increases, and heat resistance after curing of the resin composition, etc. properties may be degraded.
イミド化物(P)は、公知の方法で合成することができる。例えば、合成に用いる(A)成分および(B)成分を溶剤に溶解させた後、窒素等の不活性雰囲気下、10乃至140℃で加熱撹拌することによってジアミン類と四塩基酸二無水物類との共重合反応が起こり、ポリアミック酸樹脂溶液が得られる。 The imidized product (P) can be synthesized by a known method. For example, after dissolving the components (A) and (B) used in the synthesis in a solvent, the diamines and the tetrabasic dianhydrides are obtained by heating and stirring at 10 to 140°C under an inert atmosphere such as nitrogen. A copolymerization reaction with occurs to obtain a polyamic acid resin solution.
次いで前記で得られたポリアミック酸樹脂溶液に必要により脱水剤や触媒を加え、100乃至300℃で加熱撹拌することによってイミド化反応(脱水を伴う閉環反応)が起こり、イミド化物(P)が得られる。脱水剤としてはトルエン及びキシレン等が、触媒としては3級アミン、及び脱水触媒を用いることができる。3級アミンとしては、複素環式の3級アミンが好ましく、例えば、ピリジン、ピコリン、キノリン、及びイソキノリンなどを挙げられる。脱水触媒としては、例えば、無水酢酸、プロピオン酸無水物、n-酪酸無水物、安息香酸無水物、及びトリフルオロ酢酸無水物等が挙げられる。尚、イミド化物(P)を合成する際の反応時間は反応温度により大きく影響されるが、反応の進行に伴う粘度上昇が平衡に達し、最大の分子量が得られるまで反応を行うことが好ましく、通常数分間乃至30時間である。 Then, if necessary, a dehydrating agent or a catalyst is added to the polyamic acid resin solution obtained above, and the mixture is heated and stirred at 100 to 300° C. to cause an imidization reaction (a ring closure reaction accompanied by dehydration) to obtain an imidized product (P). be done. Toluene, xylene and the like can be used as dehydrating agents, and tertiary amines and dehydrating catalysts can be used as catalysts. Preferred tertiary amines are heterocyclic tertiary amines such as pyridine, picoline, quinoline, and isoquinoline. Dehydration catalysts include, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. The reaction time for synthesizing the imidized compound (P) is greatly affected by the reaction temperature. Usually from a few minutes to 30 hours.
上記の例はポリアミック酸を経由してイミド化物(P)を合成する方法であるが、合成に用いる(A)成分および(B)成分を溶剤に溶解させた後、必要により脱水剤や触媒を加え、100乃至300℃で加熱撹拌することによって共重合反応とイミド化反応を一括で行い、イミド化物(P)を得てもよい。 The above example is a method of synthesizing the imidized product (P) via polyamic acid. After dissolving the components (A) and (B) used in the synthesis in a solvent, a dehydrating agent and a catalyst are added as necessary. In addition, the copolymerization reaction and the imidization reaction may be performed together by heating and stirring at 100 to 300° C. to obtain the imidized product (P).
イミド化物(P)の合成時に用い得る溶剤としては、メチルエチルケトン、メチルプロピルケトン、メチルイソプロピルケトン、メチルブチルケトン、メチルイソブチルケトン、メチルn-ヘキシルケトン、ジエチルケトン、ジイソプロピルケトン、ジイソブチルケトン、シクロペンタノン、シクロヘキサノン、メチルシクロヘキサノン、アセチルアセトン、γ-ブチロラクトン、ジアセトンアルコール、シクロヘキセン-1-オン、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、テトラヒドロピラン、エチルイソアミルエーテル、エチル-t-ブチルエーテル、エチルベンジルエーテル、クレジルメチルエーテル、アニソール、フェネトール、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸アミル、酢酸イソアミル、酢酸2-エチルヘキシル、酢酸シクロヘキシル、酢酸メチルシクロヘキシル、酢酸ベンジル、アセト酢酸メチル、アセト酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸ブチル、プロピオン酸ベンジル、酪酸メチル、酪酸エチル、酪酸イソプロピル、酪酸ブチル、酪酸イソアミル、乳酸メチル、乳酸エチル、乳酸ブチル、イソ吉草酸エチル、イソ吉草酸イソアミル、シュウ酸ジエチル、シュウ酸ジブチル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、サリチル酸メチル、N-メチルピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、ジメチルスルホキシド等が挙げられるが、これらに限定されるものではない。これらは1種を用いてもよく、2種以上を混合して用いてもよい。 Solvents that can be used in synthesizing the imidized compound (P) include methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, and cyclopentanone. , cyclohexanone, methylcyclohexanone, acetylacetone, γ-butyrolactone, diacetone alcohol, cyclohexene-1-one, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, ethyl isoamyl ether, ethyl-t-butyl ether, ethyl benzyl ether , cresyl methyl ether, anisole, phenetole, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, aceto Methyl acetate, ethyl acetoacetate, methyl propionate, ethyl propionate, butyl propionate, benzyl propionate, methyl butyrate, ethyl butyrate, isopropyl butyrate, butyl butyrate, isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate, isovaleric acid Ethyl, isoamyl isovalerate, diethyl oxalate, dibutyl oxalate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Examples include, but are not limited to, sulfoxides. These may be used alone or in combination of two or more.
好ましい溶剤の使用量は、得られる樹脂の粘度や使途により適宜調整されるべきものであるが、好ましくは固形分含有率60乃至10質量%、より好ましくは50乃至20質量%である。 The preferred amount of the solvent to be used should be appropriately adjusted depending on the viscosity of the resin to be obtained and the intended use.
イミド化物(P)合成時の脱水反応を促進させるために、触媒を使用することが好ましく、該触媒の使用量は、(B)成分のモル数の2倍(脱水縮合により生じる水のモル数)の1乃至30%が好ましく、より好ましくは5乃至15%である。使用しうる触媒の具体例としては、トリエチルアミン、ピリジン等既知一般の塩基性触媒等が挙げられる。中でも、沸点が低く、残留しにくい点からトリエチルアミンが好ましい。 In order to promote the dehydration reaction during the synthesis of the imidized product (P), it is preferable to use a catalyst. ), preferably 1 to 30%, more preferably 5 to 15%. Specific examples of usable catalysts include known basic catalysts such as triethylamine and pyridine. Among them, triethylamine is preferable because it has a low boiling point and does not easily remain.
次に、イミド化物(P)と(C)成分との反応物である(D)成分について説明する。
(D)成分は、イミド化物(P)の有するフェノール性水酸基の一部または全部に、(C)成分を介してエチレン性不飽和二重結合基を導入した構造のポリイミド樹脂である。(D)成分の粘度はエチレン性不飽和二重結合基導入前のイミド化物(P)よりも下がるため、(D)成分を含む樹脂組成物からなる樹脂層の銅箔に対するラミネート性が向上する傾向にある。また、エチレン性不飽和二重結合基は互いに又は後述する熱硬化性樹脂(F)の有する様々な官能基と反応し得るため、樹脂組成物の硬化物の優れた耐熱性と接着性が両立する。
Next, the (D) component, which is the reaction product of the imidized product (P) and the (C) component, will be described.
The component (D) is a polyimide resin having a structure in which an ethylenically unsaturated double bond group is introduced via the component (C) into some or all of the phenolic hydroxyl groups of the imidized product (P). Since the viscosity of the component (D) is lower than that of the imidized product (P) before the introduction of the ethylenically unsaturated double bond group, the laminating property of the resin layer made of the resin composition containing the component (D) to the copper foil is improved. There is a tendency. In addition, since the ethylenically unsaturated double bond groups can react with each other or with various functional groups of the thermosetting resin (F) described later, the cured product of the resin composition has excellent heat resistance and adhesiveness. do.
イミド化物(P)との反応に用いられる(C)成分は、フェノール性水酸基と反応し得る官能基とエチレン性不飽和二重結合基を有する化合物であれば特に限定されない。
(C)成分が有するフェノール性水酸基と反応し得る官能基としては、例えばイソシアネート基、カルボン酸クロリド基、酸無水物基、エポキシ基、シリルクロリド基、ハロゲン化アルキル基、エステル基、スルホニルクロリド基及びカルボキシル基等が挙げられる。特に(C)成分からの脱離基由来の残留不純物が生じない点から、イソシアネート基が好ましい。
尚、(C)成分が有するエチレン性不飽和二重結合基は、C=C結合であれば特に限定されない。
The (C) component used for the reaction with the imidized product (P) is not particularly limited as long as it is a compound having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group.
Examples of functional groups capable of reacting with phenolic hydroxyl groups of component (C) include isocyanate groups, carboxylic acid chloride groups, acid anhydride groups, epoxy groups, silyl chloride groups, halogenated alkyl groups, ester groups, and sulfonyl chloride groups. and a carboxyl group. In particular, an isocyanate group is preferred because residual impurities derived from the leaving group from component (C) do not occur.
In addition, the ethylenically unsaturated double bond group of the component (C) is not particularly limited as long as it is a C═C bond.
尚、(A)成分のモル数MAと(B)成分のモル数MBがMA/MB>1の関係を満たす量の(A)成分と(B)成分を共重合させ得られるイミド化物(P)は末端がアミノ基となるため、フェノール性水酸基と反応し得る官能基がイソシアネート基、カルボン酸クロリド基、酸無水物基、エポキシ基、シリルクロリド基、ハロゲン化アルキル基、エステル基、スルホニルクロリド基又はカルボキシル基の(C)成分は、イミド化物(P)の末端アミノ基とも反応し得る。 Incidentally, the imidized product (P ) has an amino group at the end, so the functional groups that can react with phenolic hydroxyl groups are isocyanate group, carboxylic acid chloride group, acid anhydride group, epoxy group, silyl chloride group, halogenated alkyl group, ester group, sulfonyl chloride The group or carboxyl group (C) component can also react with the terminal amino group of the imidide (P).
また、(A)成分のモル数MAと(B)成分のモル数MBがMA/MB<1の関係を満たす量の(A)成分と(B)成分を共重合させ得られるイミド化物(P)は末端が酸無水物基となるため、フェノール性水酸基と反応しうる官能基がイソシアネート基、エポキシ基又はカルボキシル基の(C)成分は、イミド化物(P)の末端酸無水物基とも反応し得る。 Further, the imidized product (P ) has an acid anhydride group at the end, so the functional group that can react with the phenolic hydroxyl group is an isocyanate group, an epoxy group, or a carboxyl group. can.
(C)成分の具体例としては、カレンズMOI(昭和電工株式会社製)、カレンズAOI、カレンズMOI-BM、カレンズMOI-BP、カレンズBEI、カレンズMOI-EG、AOI-VM、メタクリル酸クロリド、アクリル酸クロリド、マレイミドカプロン酸クロリド、臭化アリル、ヨウ化アリル、塩化アリル、4-クロロ-1-ブテン、4-ブロモ-1-ブテン、クロトノイルクロリド、シンナモイルクロリドなどが挙げられる。 Specific examples of component (C) include Karenz MOI (manufactured by Showa Denko KK), Karenz AOI, Karenz MOI-BM, Karenz MOI-BP, Karenz BEI, Karenz MOI-EG, AOI-VM, methacrylic acid chloride, and acrylic. Acid chloride, maleimidocaproic chloride, allyl bromide, allyl iodide, allyl chloride, 4-chloro-1-butene, 4-bromo-1-butene, crotnoyl chloride, cinnamoyl chloride and the like.
イミド化物(P)と(C)成分との反応物である(D)成分は、公知の方法で合成することができる。例えば、イミド化物(P)の樹脂溶液に、所定量の(C)成分を混合し、80℃乃至150℃で反応させることにより合成できる。 Component (D), which is a reaction product of imidized product (P) and component (C), can be synthesized by a known method. For example, it can be synthesized by mixing a predetermined amount of component (C) with a resin solution of imidized compound (P) and reacting the mixture at 80°C to 150°C.
イミド化物(P)と(C)成分の反応を進行させるために各種触媒を使用してもよい。触媒は既知の無機酸、有機酸、無機塩基、有機塩基などが使用できる。 Various catalysts may be used to promote the reaction between the imidized product (P) and the component (C). Known inorganic acids, organic acids, inorganic bases, organic bases and the like can be used as catalysts.
(D)成分の合成に用いられる(C)成分のモル数をMC、イミド化物(P)のフェノール性水酸基のモル数をMAB、イミド化物(P)の末端官能基のモル数をMPとした場合、MC/(MAB+MP)の値が0.3を超えて1未満であることが好ましく、0.5を超えて1未満であることがより好ましい。MC/(MAB+MP)が1を超える場合は、未反応の(C)成分により樹脂組成物の硬化物の耐熱性が悪化する。また、MC/(MAB+MP)が0.3以下の場合は、(C)成分と反応しないフェノール性水酸基の水素結合によりポリイミド樹脂溶液の粘度が上昇し、ラミネート性が下がる傾向にある上、樹脂組成物の硬化物の基材接着性が低下する傾向にある。 MC is the number of moles of component (C) used in the synthesis of component (D), MAB is the number of moles of phenolic hydroxyl groups in imidized product (P), and MP is the number of moles of terminal functional groups of imidized product (P). In this case, the value of MC/(MAB+MP) is preferably greater than 0.3 and less than 1, more preferably greater than 0.5 and less than 1. When MC/(MAB+MP) exceeds 1, the unreacted component (C) deteriorates the heat resistance of the cured product of the resin composition. Further, when MC/(MAB+MP) is 0.3 or less, the viscosity of the polyimide resin solution increases due to the hydrogen bonding of the phenolic hydroxyl groups that do not react with the component (C), and the lamination property tends to decrease. The substrate adhesion of the cured product tends to decrease.
次に、(E)成分について説明する。
(E)成分のBET法における比表面積は、1.0乃至20m2/gであることが好ましい。比表面積が上記の範囲内の(E)成分を用いることにより、樹脂層中の(E)成分の分散性が改善されて樹脂層の硬化物の可撓性が向上すると共に、シリカと樹脂成分の硬化物との接着強度が向上して、外部からの応力による樹脂層の凝集破壊が起こり難くなる。
Next, the (E) component will be explained.
The BET specific surface area of component (E) is preferably 1.0 to 20 m 2 /g. By using the component (E) having a specific surface area within the above range, the dispersibility of the component (E) in the resin layer is improved, the flexibility of the cured product of the resin layer is improved, and the silica and the resin component are improved. The adhesive strength with the cured product of is improved, and cohesive failure of the resin layer due to external stress is less likely to occur.
本発明の樹脂付き銅箔の樹脂層となる樹脂組成物における(E)成分の含有量は、(D)成分の固形分に対し5乃至50質量%であることが好ましく、10乃至45質量%であることがより好ましく、15乃至35質量%であることが更に好ましい。(E)成分の含有量を前記の範囲とすることにより、樹脂層の硬化物と銅箔との接着性が向上したり、樹脂層の硬化物の可撓性が高くなる。 The content of component (E) in the resin composition that forms the resin layer of the resin-coated copper foil of the present invention is preferably 5 to 50% by mass, preferably 10 to 45% by mass, based on the solid content of component (D). and more preferably 15 to 35% by mass. By setting the content of the component (E) within the above range, the adhesion between the cured resin layer and the copper foil is improved, and the cured resin layer has increased flexibility.
(E)成分の平均粒子径は、0.3乃至5.0μmであることが好ましい。(E)成分の平均粒子径を前記の範囲とすることにより、樹脂層への気泡の混入を低減できると共に、樹脂層が銅箔の凹凸に効率よく入り込んで樹脂層の硬化物と銅箔との接着性が向上する。
尚、本明細書における(E)成分の平均粒子径は、レーザー回折散乱方式の粒度分布測定装置を用いて測定した値を意味する。
The average particle size of component (E) is preferably 0.3 to 5.0 μm. By setting the average particle size of the component (E) within the above range, it is possible to reduce the inclusion of air bubbles in the resin layer, and the resin layer efficiently penetrates into the unevenness of the copper foil to separate the cured product of the resin layer and the copper foil. improves adhesion.
The average particle size of component (E) in the present specification means a value measured using a laser diffraction scattering type particle size distribution analyzer.
(E)成分は、シラン化合物で表面処理されていないことが好ましい。(E)成分が表面処理されていると、分散性は向上するものの、樹脂層の硬化物の耐熱性及び樹脂層の硬化物と銅箔との接着性の向上効果が充分に得られないことがある。 Component (E) is preferably not surface-treated with a silane compound. If the component (E) is surface-treated, the dispersibility is improved, but the effect of improving the heat resistance of the cured resin layer and the adhesion between the cured resin layer and the copper foil cannot be sufficiently obtained. There is
(E)成分は、球状であることが好ましい。この場合、樹脂層が銅箔表面の凸凹に効率よく入り込んで、樹脂層の硬化物と銅箔との接着性を一層高めることができる。 Component (E) is preferably spherical. In this case, the resin layer efficiently penetrates into the unevenness of the surface of the copper foil, and the adhesion between the cured resin layer and the copper foil can be further enhanced.
次に(F)成分について説明する。
(F)成分の具体例としては、エポキシ樹脂、マレイミド樹脂、カルボジイミド樹脂、ベンゾオキサジン化合物及びエチレン性不飽和基を有する化合物等が挙げられる。これらの樹脂または化合物は、本発明の樹脂付き銅箔の有する樹脂層を硬化させて得られる銅張積層体の物性および用途に応じて、1種類単独または2種類以上を適宜混合して使用することができる。
本発明においては、(D)成分に(F)成分を併用することにより、樹脂組成物からなる樹脂層の硬化物に熱安定性と高い接着性を付与することができる。その際、(D)成分の末端官能基(アミノ基又は酸無水物基)または(C)成分由来のエチレン性不飽和二重結合基と、(F)成分が反応することが好ましい。
Next, the (F) component will be explained.
Specific examples of component (F) include epoxy resins, maleimide resins, carbodiimide resins, benzoxazine compounds and compounds having ethylenically unsaturated groups. These resins or compounds may be used alone or in admixture of two or more depending on the physical properties and application of the copper-clad laminate obtained by curing the resin layer of the resin-coated copper foil of the present invention. be able to.
In the present invention, by using component (D) in combination with component (F), it is possible to impart thermal stability and high adhesiveness to the cured product of the resin layer composed of the resin composition. At that time, it is preferred that the terminal functional group (amino group or acid anhydride group) of component (D) or the ethylenically unsaturated double bond group derived from component (C) react with component (F).
(F)成分としては、樹脂組成物の硬化物の耐熱性や接着性が特に優れる点から、マレイミド樹脂又はエチレン性不飽和基を有する化合物が好ましい。
尚、ポリアミック酸樹脂の合成に用いられる(A)成分のモル数をMA、(B)成分のモル数をMB、(C)成分のモル数をMC、イミド化物(P)の末端官能基のモル数をMP、(a1)成分のモル数をMa1とした場合に、MA/MBの値が1を超え、かつMC/(MP+Ma1)の値が0を超えて1未満であるポリイミド樹脂に関しては、熱硬化性樹脂として、エポキシ樹脂を使用することも好ましい。
As the component (F), a maleimide resin or a compound having an ethylenically unsaturated group is preferable because the heat resistance and adhesiveness of the cured product of the resin composition are particularly excellent.
In addition, the number of moles of component (A) used for the synthesis of the polyamic acid resin is MA, the number of moles of component (B) is MB, the number of moles of component (C) is MC, and the number of terminal functional groups of the imide (P) is When the number of moles is MP and the number of moles of component (a1) is Ma1, the value of MA/MB exceeds 1, and the value of MC/(MP+Ma1) exceeds 0 and is less than 1. It is also preferable to use an epoxy resin as the thermosetting resin.
また、(F)成分は、樹脂組成物を溶剤に溶解してワニスとした際の粘度上昇が抑制できる観点から、分子量が100乃至50,000であることが好ましい。尚、本明細書における分子量とは、ゲル浸透クロマトグラフィー(GPC)法による、ポリスチレンスタンダードの重量平均分子量を意味する。 In addition, the component (F) preferably has a molecular weight of 100 to 50,000 from the viewpoint of suppressing an increase in viscosity when the resin composition is dissolved in a solvent to form a varnish. The term "molecular weight" as used herein means the weight-average molecular weight of a polystyrene standard determined by gel permeation chromatography (GPC).
(F)成分としてのマレイミド樹脂は、一分子中にマレイミド基を二つ以上有するものであれば特に限定されない。
一分子中にマレイミド基を二つ以上有するマレイミド樹脂の具体例として、3,4,4’-トリアミノジフェニルメタン、トリアミノフェノールなどと無水マレイン酸との反応で得られる多官能マレイミド化合物、トリス-(4-アミノフェニル)-ホスフェート、トリス(4-アミノフェニル)-ホスフェート、トス(4-アミノフェニル)-チオホスフェートと無水マレイン酸との反応で得られるマレイミド化合物、トリス(4-マレイミドフェニル)メタン等のトリスマレイミド化合物、ビス(3,4-ジマレイミドフェニル)メタン、テトラマレイミドベンゾフェノン、テトラマレイミドナフタレン、トリエチレンテトラミンと無水マレイン酸との反応で得られるマレイミド等のテトラマレイミド化合物、フェノールノボラック型マレイミド樹脂、イソプロピリデンビス(フェノキシフェニルマレイミド)フェニルマレイミドアラルキル樹脂、ビフェニレン型フェニルマレイミドアラルキル樹脂等挙げられ、市販品としては、MIR-3000、MIR-5000(いずれも日本化薬株式会社製)、BMI-70、BMI-80(いずれもケイ・アイ化成株式会社製)、BMI-1000、BMI-2000、BMI-3000、(いずれも大和化成工業株式会社製)、等が挙げられる。
The maleimide resin as component (F) is not particularly limited as long as it has two or more maleimide groups in one molecule.
Specific examples of maleimide resins having two or more maleimide groups in one molecule include tris- (4-aminophenyl)-phosphate, tris(4-aminophenyl)-phosphate, maleimide compound obtained by reaction of tos(4-aminophenyl)-thiophosphate with maleic anhydride, tris(4-maleimidophenyl)methane tetramaleimide compounds such as bis(3,4-dimaleimidophenyl)methane, tetramaleimidobenzophenone, tetramaleimidonaphthalene, maleimide obtained by the reaction of triethylenetetramine and maleic anhydride, phenol novolac type maleimide resins, isopropylidenebis(phenoxyphenylmaleimide)phenylmaleimide alkyl resins, biphenylene-type phenylmaleimide alkyl resins, etc. Commercially available products include MIR-3000, MIR-5000 (both manufactured by Nippon Kayaku Co., Ltd.), BMI- 70, BMI-80 (all manufactured by KI Kasei Co., Ltd.), BMI-1000, BMI-2000, BMI-3000 (all manufactured by Daiwa Kasei Kogyo Co., Ltd.), and the like.
特に、樹脂組成物の硬化物からなる樹脂層が機械強度や難燃性等の特性に優れることから、ベンゼン環、ビフェニル環及びナフタレン環等の芳香族環を有するマレイミド樹脂が好ましく、その具体例としては、MIR-3000(日本化薬株式会社製)、MIR-5000(日本化薬株式会社製)が挙げられる。
マレイミド樹脂は、(D)成分の有するエチレン性不飽和二重結合基と反応させることを目的に加えられ、これにより樹脂組成物の硬化物からなる樹脂層の架橋密度が増加し、極性溶剤への耐性が向上すると共に、銅箔への密着性や耐熱性が向上する。
樹脂層となる樹脂組成物がマレイミド樹脂を含有する場合の硬化温度は、150乃至250℃が好ましい。硬化時間は硬化温度に依存するが、概ね数分間乃至数時間程度である。
樹脂層となる樹脂組成物におけるマレイミド樹脂の含有量は、(D)成分のエチレン性不飽和二重結合基1当量に対して、マレイミド樹脂のマレイミド基当量が0.1乃至500当量となる量が好ましい。
尚、本明細書におけるマレイミド基当量は、原料として用いたアミンのアミン当量から算出した理論マレイミド当量を意味する。
In particular, a maleimide resin having an aromatic ring such as a benzene ring, a biphenyl ring and a naphthalene ring is preferable because the resin layer composed of a cured product of the resin composition is excellent in properties such as mechanical strength and flame retardancy. Examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) and MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.).
The maleimide resin is added for the purpose of reacting with the ethylenically unsaturated double bond group of the component (D), thereby increasing the crosslink density of the resin layer composed of the cured product of the resin composition and resistance to the copper foil is improved, and adhesion to the copper foil and heat resistance are improved.
When the resin composition that forms the resin layer contains a maleimide resin, the curing temperature is preferably 150 to 250°C. The curing time depends on the curing temperature, but is generally several minutes to several hours.
The content of the maleimide resin in the resin composition for the resin layer is such that the maleimide group equivalent of the maleimide resin is 0.1 to 500 equivalents with respect to 1 equivalent of the ethylenically unsaturated double bond groups of the component (D). is preferred.
In addition, the maleimide group equivalent in this specification means the theoretical maleimide equivalent calculated from the amine equivalent of the amine used as a raw material.
(F)成分としてのエポキシ樹脂は、一分子中にエポキシ基を二つ以上有するものであれば特に限定されないが、樹脂組成物の硬化物からなる樹脂層が機械強度や難燃性等の特性に優れることから、ベンゼン環、ビフェニル環及びナフタレン環等の芳香族環を有するエポキシ樹脂が好ましく、その具体例としては、jER828(三菱ケミカル株式会社製)、NC-3000、XD-1000(いずれも日本化薬株式会社製)等が挙げられる。
エポキシ樹脂は、(D)成分の末端アミノ基若しくは酸無水物基と反応させることを目的に加えられ、これにより樹脂組成物の硬化物からなる樹脂層の架橋密度が増加し、極性溶剤への耐性が向上すると共に、銅箔への密着性や耐熱性が向上する。
エポキシ樹脂を含有する樹脂組成物の硬化温度は、150乃至250℃が好ましい。硬化時間は硬化温度に依存するが、概ね数分間乃至数時間程度である。
The epoxy resin as the component (F) is not particularly limited as long as it has two or more epoxy groups in one molecule. Epoxy resins having aromatic rings such as benzene rings, biphenyl rings and naphthalene rings are preferred because they are excellent in manufactured by Nippon Kayaku Co., Ltd.) and the like.
The epoxy resin is added for the purpose of reacting with the terminal amino group or acid anhydride group of the component (D), thereby increasing the cross-linking density of the resin layer composed of the cured product of the resin composition and making it resistant to polar solvents. The resistance is improved, and the adhesion to the copper foil and heat resistance are improved.
The curing temperature of the resin composition containing the epoxy resin is preferably 150 to 250°C. The curing time depends on the curing temperature, but is generally several minutes to several hours.
樹脂層となる樹脂組成物がエポキシ樹脂を含有する場合のエポキシ樹脂の含有量は、(D)成分の有する末端アミノ基の活性水素及び末端酸無水物基1当量に対するエポキシ樹脂のエポキシ基当量が0.1乃至500当量となる量が好ましい。
尚、本明細書におけるエポキシ基当量は、JIS K-7236に記載された方法で測定した値を意味する。
When the resin composition for the resin layer contains an epoxy resin, the content of the epoxy resin is such that the epoxy group equivalent of the epoxy resin with respect to the active hydrogen of the terminal amino group and the terminal acid anhydride group of the component (D) is An amount of 0.1 to 500 equivalents is preferred.
Incidentally, the epoxy group equivalent in this specification means the value measured by the method described in JIS K-7236.
(F)成分としてのエチレン性不飽和基を有する化合物は、一分子中にエチレン性不飽和基を一つ以上有するものであれば特に限定されない。
エチレン性不飽和基を有する化合物の具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、ラウリル(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレートモノメチルエーテル、フェニルエチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、ブタンジオールジ(メタ)アクリレート、ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ノナンジオールジ(メタ)アクリレート、グリコールジ(メタ)アクリレート、ジエチレンジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、トリス(メタ)アクリロイルオキシエチルイソシアヌレート、ポリプロピレングリコールジ(メタ)アクリレート、アジピン酸エポキシジ(メタ)アクリレート、ビスフェノールエチレンオキサイドジ(メタ)アクリレート、水素化ビスフェノールエチレンオキサイド(メタ)アクリレート、ビスフェノールジ(メタ)アクリレート、ε-カプロラクトン変性ヒドロキシピバリン酸ネオペングリコールジ(メタ)アクリレート、ε-カプロラクトン変性ジペンタエリスリトールヘキサ(メタ)アクリレート、ε-カプロラクトン変性ジペンタエリスリトールポリ(メタ)アクリレート、ジペンタエリスリトールポリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリエチロールプロパントリ(メタ)アクリレート、及びそのエチレンオキサイド付加物;ペンタエリスリトールトリ(メタ)アクリレート、及びそのエチレンオキサイド付加物;ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、及びそのエチレンオキサイド付加物等が挙げられる。
The compound having an ethylenically unsaturated group as the component (F) is not particularly limited as long as it has one or more ethylenically unsaturated groups in one molecule.
Specific examples of compounds having an ethylenically unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) Acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate ) acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, glycol di(meth)acrylate, diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate , polypropylene glycol di(meth)acrylate, adipate epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone-modified hydroxypivalic acid Neopen glycol di(meth)acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate ) acrylate, triethylolpropane tri(meth)acrylate and its ethylene oxide adduct; pentaerythritol tri(meth)acrylate and its ethylene oxide adduct; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate , and ethylene oxide adducts thereof.
また、この他にも、(メタ)アクリロイル基とウレタン結合を同一分子内に併せ持つウレタン(メタ)アクリレート類;(メタ)アクリロイル基とエステル結合を同一分子内に併せ持つポリエステル(メタ)アクリレート類;エポキシ樹脂から誘導され、(メタ)アクリロイル基を併せ持つエポキシ(メタ)アクリレート類;これらの結合が複合的に用いられている反応性オリゴマー等もエチレン性不飽和基を有する化合物の具体例として挙げられる。 In addition to these, urethane (meth)acrylates having both a (meth)acryloyl group and a urethane bond in the same molecule; polyester (meth)acrylates having both a (meth)acryloyl group and an ester bond in the same molecule; epoxy Epoxy (meth) acrylates derived from resins and having (meth) acryloyl groups; reactive oligomers in which these bonds are used in combination are also specific examples of compounds having ethylenically unsaturated groups.
ウレタン(メタ)アクリレート類とは、水酸基含有(メタ)アクリレートとポリイソシアネート、必要に応じて用いられるその他アルコール類との反応物が挙げられる。例えば、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート類;グリセリンモノ(メタ)アクリレート、グリセリンジ(メタ)アクリレート等のグリセリン(メタ)アクリレート類;ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の糖アルコール(メタ)アクリレート類と、トルエンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、キシレンジイソシアネート、水添キシレンジイソシアネート、ジシクロヘキサンメチレンジイソシアネート、及びそれらのイソシアヌレート、ビュレット反応物等のポリイソシアネート等を反応させた、ウレタン(メタ)アクリレート類が挙げられる。 Urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates, polyisocyanates, and other alcohols used as necessary. For example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; ) acrylates; sugar alcohol (meth)acrylates such as pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and toluene diisocyanate , hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and their isocyanurates, burette reaction products, etc., reacted with polyisocyanates, etc., urethane ( meth)acrylates.
ポリエステル(メタ)アクリレート類とは、例えば、カプロラクトン変性2-ヒドロキシエチル(メタ)アクリレート、エチレンオキサイド及び/又はプロピレンオキサイド変性フタル酸(メタ)アクリレート、エチレンオキサイド変性コハク酸(メタ)アクリレート、カプロラクトン変性テトラヒドロフルフリル(メタ)アクリレート等の単官能(ポリ)エステル(メタ)アクリレート類;ヒドロキシピバリン酸エステルネオペンチルグリコールジ(メタ)アクリレート、カプロラクトン変性ヒドロキシピバリン酸エステルネオペンチルグリコールジ(メタ)アクリレート、エピクロルヒドリン変性フタル酸ジ(メタ)アクリレート等のジ(ポリ)エステル(メタ)アクリレート類;トリメチロールプロパン又はグリセリン1モルに1モル以上のε-カプロラクトン、γ-ブチロラクトン、δ-バレロラクトン等の環状ラクトン化合物を付加して得たトリオールのモノ、ジ又はトリ(メタ)アクリレートが挙げられる。 Polyester (meth)acrylates include, for example, caprolactone-modified 2-hydroxyethyl (meth)acrylate, ethylene oxide and/or propylene oxide-modified phthalic acid (meth)acrylate, ethylene oxide-modified succinic acid (meth)acrylate, caprolactone-modified tetrahydro Monofunctional (poly)ester (meth)acrylates such as furfuryl (meth)acrylate; hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, epichlorohydrin-modified Di (poly) ester (meth) acrylates such as phthalic acid di (meth) acrylate; 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone per 1 mol of trimethylolpropane or glycerin Mono-, di- or tri(meth)acrylates of adducted triols may be mentioned.
また、ペンタエリスリトール、ジメチロールプロパン、トリメチロールプロパン、又はテトラメチロールプロパン1モルに、1モル以上のε-カプロラクトン、γ-ブチロラクトン、δ-バレロラクトン等の環状ラクトン化合物を付加して得たトリオールのモノ、ジ、トリ又はテトラ(メタ)アクリレート;ジペンタエリスリトール1モルに1モル以上のε-カプロラクトン、γ-ブチロラクトン、δ-バレロラクトン等の環状ラクトン化合物を付加して得たトリオールのモノ、若しくはポリ(メタ)アクリレートのトリオール、テトラオール、ペンタオール又はヘキサオール等の多価アルコールのモノ(メタ)アクリレート又はポリ(メタ)アクリレートが挙げられる。 Also, a triol obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mol of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane. mono-, di-, tri-, or tetra-(meth)acrylates; mono-triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone to 1 mol of dipentaerythritol, or Examples include mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols or hexaols of poly(meth)acrylates.
更に、(ポリ)エチレングリコール、(ポリ)プロピレングリコール、(ポリ)テトラメチレングリコール、(ポリ)ブチレングリコール、3-メチル-1,5-ペンタンジオール、ヘキサンジオール等のジオール成分と、マレイン酸、フマル酸、コハク酸、アジピン酸、フタル酸、イソフタル酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸、ダイマー酸、セバチン酸、アゼライン酸、5-ナトリウムスルホイソフタル酸等の多塩基酸、及びこれらの無水物との反応物であるポリエステルポリオールの(メタ)アクリレート;ジオール成分と多塩基酸及びこれらの無水物とε-カプロラクトン、γ-ブチロラクトン、δ-バレロラクトン等からなる環状ラクトン変性ポリエステルジオールの(メタ)アクリレート等の多官能(ポリ)エステル(メタ)アクリレート類等を挙げることができる。 Furthermore, diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, hexanediol, maleic acid, fumaric Polybasic acids such as acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, and anhydrides thereof (meth)acrylate of polyester polyol which is the reaction product of; (meth)acrylate of cyclic lactone-modified polyester diol composed of diol component, polybasic acid and their anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. and polyfunctional (poly)ester (meth)acrylates such as
エポキシ(メタ)アクリレート類とは、エポキシ基を有する化合物と(メタ)アクリル酸とのカルボキシレート化合物である。例えば、フェノールノボラック型エポキシ(メタ)アクリレート、クレゾールノボラック型エポキシ(メタ)アクリレート、トリスヒドロキシフェニルメタン型エポキシ(メタ)アクリレート、ジシクロペンタジエンフェノール型エポキシ(メタ)アクリレート、ビスフェノールA型エポキシ(メタ)アクリレート、ビスフェノールF型エポキシ(メタ)アクリレート、ビフェノール型エポキシ(メタ)アクリレート、ビスフェノールAノボラック型エポキシ(メタ)アクリレート、ナフタレン骨格含有エポキシ(メタ)アクリレート、グリオキサール型エポキシ(メタ)アクリレート、複素環式エポキシ(メタ)アクリレート等、及びこれらの酸無水物変性エポキシアクリレート等が挙げられる。 Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. For example, phenol novolak type epoxy (meth)acrylate, cresol novolak type epoxy (meth)acrylate, trishydroxyphenylmethane type epoxy (meth)acrylate, dicyclopentadiene phenol type epoxy (meth)acrylate, bisphenol A type epoxy (meth)acrylate. , bisphenol F type epoxy (meth)acrylate, biphenol type epoxy (meth)acrylate, bisphenol A novolac type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy ( meth)acrylates, and acid anhydride-modified epoxy acrylates thereof.
例えば、エチルビニルエーテル、プロピルビニルエーテル、ヒドロキシエチルビニルエーテル、エチレングリコールジビニルエーテル等のビニルエーテル類;スチレン、メチルスチレン、エチルスチレン、ジビニルベンゼン等のスチレン類やトリアリルイソシアヌレート、トリメタアリルイソシアヌレート、及びビスアリルナジイミド等のビニル基を有する化合物も、エチレン性不飽和基を有する化合物の具体例として挙げられる。 For example, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; A compound having a vinyl group such as lunadiimide is also included as a specific example of the compound having an ethylenically unsaturated group.
エチレン性不飽和基を有する化合物としては、市販品を利用することができ、例えば、KAYARAD(登録商標)ZCA-601H(商品名、日本化薬(株)製)、TrisP-PAエポキシアクリレート化合物のプロピレングリコールモノメチルエーテルアセテート(日本化薬(株)製KAYARAD(登録商標)ZCR-6007H(商品名)KAYARAD(登録商標)ZCR-6001H(商品名)、KAYARAD(登録商標)ZCR-6002H(商品名)、及びKAYARAD(登録商標)ZCR-6006H(商品名)が挙げられる。これらのエチレン性不飽和基を有する化合物は、1種単独又は2種以上を適宜混合して使用することも可能である。 As the compound having an ethylenically unsaturated group, commercially available products can be used. Propylene glycol monomethyl ether acetate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) ZCR-6007H (trade name), KAYARAD (registered trademark) ZCR-6001H (trade name), KAYARAD (registered trademark) ZCR-6002H (trade name) , and KAYARAD (registered trademark) ZCR-6006H (trade name) These compounds having an ethylenically unsaturated group can be used singly or in admixture of two or more.
樹脂層となる樹脂組成物におけるエチレン性不飽和基を有する化合物の含有量は、(D)成分のエチレン性不飽和二重結合基当量に対して0.1乃至500当量となる量が好ましい。
尚、本明細書におけるエチレン性不飽和二重結合基当量は、原料から算出した理論エチレン性不飽和二重結合基当量を意味する。
The content of the compound having an ethylenically unsaturated group in the resin composition forming the resin layer is preferably 0.1 to 500 equivalents relative to the ethylenically unsaturated double bond group equivalent of component (D).
In addition, the ethylenically unsaturated double bond group equivalent in this specification means the theoretical ethylenically unsaturated double bond group equivalent calculated from the raw material.
次に(G)成分について説明する。
(G)成分は(F)成分の硬化反応を促進するものであれば特に限定されず、(F)成分の硬化剤として従来公知のものを使用可能である。(G)成分は1種類のみを用いてもよく、2種類以上を併用してもよい。
Next, the (G) component will be explained.
Component (G) is not particularly limited as long as it accelerates the curing reaction of component (F), and conventionally known curing agents for component (F) can be used. (G) A component may use only 1 type and may use 2 or more types together.
(F)成分がマレイミド樹脂の場合、(G)成分として公知のアミン化合物やチオール化合物、ラジカル開始剤を使用できる。
アミノ化合物の具体例としては、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、m-キシレンジアミン、トリメチルヘキサメチレンジアミン、2-メチルペンタメチレンジアミン、ジエチルアミノプロピルアミン、イソホロンジアミン、1,3-ビスアミノメチルシクロヘキサン、ビス(4-アミノシクロヘキシル)メタン、ビス(4-アミノ-3-メチルシクロヘキシル)メタン、ノルボルネンジアミン、1,2-ジアミノシクロヘキサン、ジアミノジフェニルメタン、メタフェニレンジアミン、ジアミノジフェニルスルホン、ジシアンジアミド、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン、N-アミノエチルピペラジン、アニリン・ホルマリン樹脂等が挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく、2種以上併用してもよい。樹脂層となる樹脂組成物が(F)成分としてマレイミド樹脂を含有する場合のアミン化合物の添加量は、質量比で(F)成分の好ましくは5倍以下、より好ましくは2倍以下の範囲である。
また、チオール化合物の具体例としては、トリメチロールプロパントリス(3-メルカプトプロピオネート)、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)、テトラエチレングリコールビス(3-メルカプトプロピオネート)、ジペンタエリスリトルヘキサキス(3-メルカプトプロピオネート)、トリス-[(3-メルカプトプロピオニルオキシ)-エチル]-イソシアネート等が挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく、2種以上併用してもよい。樹脂層となる樹脂組成物が(F)成分としてマレイミド樹脂を含有する場合のチオール化合物の添加量は、質量比で本発明の(F)成分の好ましくは5倍以下、より好ましくは2倍以下の範囲である。
また、ラジカル開始剤の具体例としては、ジクミルパーオキサイド及びジブチルパーオキサイド等の過酸化物類、2,2’-アゾビス(イソブチロニトリル)及び2,2’-アゾビス(2,4-ジメチルバレロニトリル)等のアゾ化合物類等が挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく、2種以上併用してもよい。樹脂層となる樹脂組成物が(F)成分としてマレイミド樹脂を含有する場合のラジカル開始剤の添加量は、マレイミド樹脂に対して0.1乃至10質量%である。
特に反応速度と誘電特性の観点から、ラジカル開始剤を使用することが好ましい。
When the (F) component is a maleimide resin, known amine compounds, thiol compounds and radical initiators can be used as the (G) component.
Specific examples of amino compounds include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, and 1,3-bisaminomethyl. Cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, dicyandiamide, polyoxypropylene Diamine, polyoxypropylenetriamine, N-aminoethylpiperazine, aniline-formalin resin, etc., but not limited to these. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains a maleimide resin as the component (F), the amount of the amine compound added is preferably 5 times or less, more preferably 2 times or less, that of the component (F) in mass ratio. be.
Further, specific examples of thiol compounds include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipenta Examples include, but are not limited to, erythritol hexakis(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanate, and the like. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains a maleimide resin as the component (F), the amount of the thiol compound added is preferably 5 times or less, more preferably 2 times or less, that of the component (F) of the present invention in mass ratio. is in the range.
Further, specific examples of radical initiators include peroxides such as dicumyl peroxide and dibutyl peroxide, 2,2′-azobis(isobutyronitrile) and 2,2′-azobis(2,4- dimethylvaleronitrile) and the like, but are not limited to these. These may be used alone or in combination of two or more. When the resin composition forming the resin layer contains a maleimide resin as the component (F), the amount of the radical initiator added is 0.1 to 10% by mass based on the maleimide resin.
In particular, from the viewpoint of reaction rate and dielectric properties, it is preferable to use a radical initiator.
(F)成分がエポキシ樹脂の場合、(G)成分として公知のイミダゾール化合物やホスフィン化合物、フェノール樹脂、アミノ化合物が使用できる。
イミダゾール化合物及びホスフィン化合物の具体例としては、2-メチルイミダゾール、2-エチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール及び2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール等のイミダゾ-ル類、2-(ジメチルアミノメチル)フェノール及び1,8-ジアザ-ビシクロ(5,4,0)ウンデセン-7等の第3級アミン類、トリフェニルホスフィン等のホスフィン類、オクチル酸スズ等の金属化合物等が挙げられるこれらに限定されるものではない。これらは単独で用いてもよく、2種以上併用してもよい。樹脂層となる樹脂組成物が(F)成分としてエポキシ樹脂を含有する場合のイミダゾール化合物又はホスフィン化合物の添加量は、エポキシ樹脂に対して0.1乃至10質量%である。
また、フェノール樹脂の具体例としてはビスフェノール類(ビスフェノールA、ビスフェノールF、ビスフェノールS、ビフェノール、ビスフェノールAD等)、フェノール類(フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等)と各種アルデヒド(ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等)との重縮合物、フェノール類と各種ジエン化合物(ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等)との重合物、フェノール類とケトン類(アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等)との重縮合物、フェノール類と芳香族ジメタノール類(ベンゼンジメタノール、α,α,α’,α’-ベンゼンジメタノール、ビフェニルジメタノール、α,α,α’,α’-ビフェニルジメタノール等)との重縮合物、フェノール類と芳香族ジクロロメチル類(α,α’-ジクロロキシレン、ビスクロロメチルビフェニル等)との重縮合物、ビスフェノール類と各種アルデヒドの重縮合物、及びこれらの変性物が挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく2種以上を用いてもよい。樹脂層となる樹脂組成物が(F)成分としてエポキシ樹脂を含有する場合のフェノール樹脂の添加量は、エポキシ樹脂に対して質量比で(F)成分の好ましくは5倍以下、より好ましくは2倍以下の範囲である。
また、アミノ化合物の具体例としては、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、m-キシレンジアミン、トリメチルヘキサメチレンジアミン、2-メチルペンタメチレンジアミン、ジエチルアミノプロピルアミン、イソホロンジアミン、1,3-ビスアミノメチルシクロヘキサン、ビス(4-アミノシクロヘキシル)メタン、ビス(4-アミノ-3-メチルシクロヘキシル)メタン、ノルボルネンジアミン、1,2-ジアミノシクロヘキサン、ジアミノジフェニルメタン、メタフェニレンジアミン、ジアミノジフェニルスルホン、ジシアンジアミド、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン、N-アミノエチルピペラジン、アニリン・ホルマリン樹脂等が挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく、2種以上併用してもよい。樹脂層となる樹脂組成物が(F)成分としてエポキシ樹脂を含有する場合のアミン化合物の添加量は、重量比で(F)成分の好ましくは5倍以下、より好ましくは2倍以下の範囲である。
誘電特性の観点から、イミダゾール化合物やホスフィン化合物を使用することが好ましい。
When the (F) component is an epoxy resin, known imidazole compounds, phosphine compounds, phenolic resins and amino compounds can be used as the (G) component.
Specific examples of imidazole compounds and phosphine compounds include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl- imidazoles such as 5-hydroxymethylimidazole, tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7, triphenylphosphine, etc. phosphines, metal compounds such as tin octylate, and the like, but are not limited to these. These may be used alone or in combination of two or more. When the resin composition forming the resin layer contains an epoxy resin as the component (F), the amount of the imidazole compound or phosphine compound added is 0.1 to 10% by mass relative to the epoxy resin.
Specific examples of phenol resins include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene , alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensation products of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) Examples include, but are not limited to, polycondensates, polycondensates of bisphenols and various aldehydes, and modified products thereof. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains an epoxy resin as the component (F), the amount of the phenol resin added is preferably 5 times or less, more preferably 2 times the mass ratio of the component (F) to the epoxy resin. It is in the range of less than double.
Specific examples of amino compounds include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3-bis Aminomethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, dicyandiamide, poly Oxypropylenediamine, polyoxypropylenetriamine, N-aminoethylpiperazine, aniline-formalin resin and the like, but not limited to these. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains an epoxy resin as the component (F), the amount of the amine compound added is preferably 5 times or less, more preferably 2 times or less, that of the component (F) by weight. be.
From the viewpoint of dielectric properties, it is preferable to use an imidazole compound or a phosphine compound.
(F)成分がエチレン性不飽和基を有する化合物の場合、(G)成分としてラジカル開始剤を使用することが好ましい。
ラジカル開始剤の具体例としては、ジクミルパーオキサイド及びジブチルパーオキサイド等の過酸化物類、2,2’-アゾビス(イソブチロニトリル)及び2,2’-アゾビス(2,4-ジメチルバレロニトリル)等のアゾ化合物類等が挙げられるこれらに限定されるものではない。これらは単独で用いてもよく、2種以上併用してもよい。樹脂層となる樹脂組成物がエチレン性不飽和基を有する化合物を含有する場合のラジカル開始剤の添加量は、組成物中の全エチレン性不飽和基に対して0.1乃至10質量%である。
When component (F) is a compound having an ethylenically unsaturated group, it is preferred to use a radical initiator as component (G).
Specific examples of radical initiators include peroxides such as dicumyl peroxide and dibutyl peroxide, 2,2′-azobis(isobutyronitrile) and 2,2′-azobis(2,4-dimethylvalero nitrile) and other azo compounds, but are not limited to these. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains a compound having an ethylenically unsaturated group, the amount of the radical initiator added is 0.1 to 10% by mass with respect to all ethylenically unsaturated groups in the composition. be.
樹脂層となる樹脂組成物に有機溶剤を併用して、ワニス状の組成物(以下、単にワニスという)とすることができる。
併用し得る溶剤としては、例えばγ-ブチロラクトン類、N-メチルピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド及びN,N-ジメチルイミダゾリジノン等のアミド系溶剤、テトラメチレンスルフォン等のスルフォン類、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、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルモノアセテート及びプロピレングリコールモノブチルエーテル等のエーテル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン及びシクロヘキサノン等のケトン系溶剤、トルエン及びキシレンなどの芳香族系溶剤が挙げられる。
有機溶剤は、ワニス中の有機溶剤以外の成分濃度が好ましくは10乃至80質量%、より好ましくは20乃至70質量%となる範囲で使用する。
A varnish-like composition (hereinafter simply referred to as varnish) can be obtained by using an organic solvent in combination with the resin composition that forms the resin layer.
Examples of solvents that can be used in combination include γ-butyrolactones, amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and N,N-dimethylimidazolidinone, and tetramethylenesulfone. sulfones, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate and propylene glycol monobutyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone and aromatic solvents such as toluene and xylene.
The organic solvent is used in such a range that the concentration of components other than the organic solvent in the varnish is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.
樹脂層となる樹脂組成物には、必要に応じて公知の添加剤を併用してもよい。
併用し得る添加剤の具体例としては、ポリブタジエン又はこの変性物、アクリロニトリル共重合体の変性物、ポリフェニレンエーテル、ポリスチレン、ポリエチレン、ポリイミド、フッ素樹脂、マレイミド系化合物、シアネートエステル系化合物、シリコーンゲル、シリコーンオイル、並びにアルミナ、炭酸カルシウム、石英粉、アルミニウム粉末、グラファイト、タルク、クレー、酸化鉄、酸化チタン、窒化アルミニウム、アスベスト、マイカ、ガラス粉末及び比表面積が1.0乃至20m2/g以外のシリカ等の無機充填材、シランカップリング剤のような充填材の表面処理剤、離型剤、カーボンブラック、フタロシアニンブルー、フタロシアニングリーン等の着色剤、アエロジル等のチキソトロピー付与剤、シリコーン系、フッ素系のレベリング剤や消泡剤、ハイドロキノン、ハイドロキノンモノメチルエーテル、フェノール系重合禁止剤、安定剤、酸化防止剤、光重合開始剤、光塩基発生材、光酸発生剤等が挙げられる。これら添加剤の配合量は、(D)成分、(E)成分、(F)成分及び(G)成分の合計100質量部に対して好ましくは1,000質部以下、より好ましくは700質部以下の範囲であるが、本発明の効果を損なわないことが前提条件である。
You may use a well-known additive together with the resin composition used as a resin layer as needed.
Specific examples of additives that can be used in combination include polybutadiene or its modified product, modified acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compound, cyanate ester compound, silicone gel, and silicone. Oil, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder and silica with a specific surface area other than 1.0 to 20 m 2 /g Inorganic fillers such as, surface treatment agents for fillers such as silane coupling agents, release agents, coloring agents such as carbon black, phthalocyanine blue and phthalocyanine green, thixotropy imparting agents such as Aerosil, silicone-based, fluorine-based Leveling agents, antifoaming agents, hydroquinone, hydroquinone monomethyl ether, phenol polymerization inhibitors, stabilizers, antioxidants, photopolymerization initiators, photobase generators, photoacid generators and the like. The amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass, per 100 parts by mass in total of components (D), (E), (F) and (G). The following range is a precondition that the effects of the present invention are not impaired.
樹脂層となる樹脂組成物の調製方法は特に限定されないが、各成分を均一に混合するだけでもよい。各成分の混合には溶剤の不存在下では例えば押出機、ニーダ、ロールなどを使用し用い、溶剤の存在下では攪拌装置つきの反応釜などを使用する。 The method of preparing the resin composition that forms the resin layer is not particularly limited, but it is also possible to simply mix the components uniformly. For mixing each component, for example, an extruder, kneader, roll, or the like is used in the absence of a solvent, and a reactor equipped with a stirrer is used in the presence of a solvent.
次に、表面粗さ(Rz)が1.1μm以下の銅箔の粗化面又は無粗化銅箔の表面に樹脂組成物からなる樹脂層を設けて本発明の樹脂付き銅箔を得る方法を説明する。
本発明の樹脂付き銅箔は、各種公知の方法で得ることができる。具体的には、樹脂組成物を加熱し粘度を下げキャスティングする手法や、溶液を塗布し溶剤を乾燥させる手法が挙げられる。
樹脂組成物の塗工手段は特に制限されず、カーテンコーター、ロールコーター、ラミネーターなどが挙げられる。また各種レベリング手段を併用してもよい
また銅箔としては、表面粗さ(Rz)が1.1μm以下の銅箔の粗化面又は無粗化銅箔であれば各種公知のものを特に制限なく使用できる。具体的には、圧延銅箔や、電解銅箔などが挙げられる。その厚みも特に制限されず、また表面処理(粗化、防錆化)が施されたモノであってもよい。
Next, a method of obtaining a resin-coated copper foil of the present invention by providing a resin layer made of a resin composition on the roughened surface of a copper foil having a surface roughness (Rz) of 1.1 μm or less or on the surface of a non-roughened copper foil. explain.
The resin-coated copper foil of the present invention can be obtained by various known methods. Specifically, a technique of heating the resin composition to lower its viscosity and casting, and a technique of applying a solution and drying the solvent can be used.
The coating means of the resin composition is not particularly limited, and includes curtain coaters, roll coaters, laminators and the like. In addition, various leveling means may be used in combination. As the copper foil, any known copper foil having a surface roughness (Rz) of 1.1 μm or less with a roughened surface or a non-roughened copper foil is particularly limited. can be used without Specific examples include rolled copper foil and electrolytic copper foil. Its thickness is not particularly limited, and it may be one subjected to surface treatment (roughening, rust prevention).
樹脂組成物からなる樹脂層は、未硬化であってもよく、また、加熱下に部分硬化させたものであってもよい。部分硬化の樹脂層は、いわゆるBステージと呼ばれる状態にある。尚、樹脂層の厚さは限定されないが、好ましくは12乃至105μm程度である。 The resin layer made of the resin composition may be uncured or may be partially cured under heating. The partially cured resin layer is in a so-called B-stage state. Although the thickness of the resin layer is not limited, it is preferably about 12 to 105 μm.
銅箔の表面に設けられた樹脂組成物からなる樹脂層を加熱により硬化物(樹脂層)とすることにより、本発明の銅張積層体とすることができる。
樹脂組成物からなる樹脂層の硬化温度及び硬化時間は、(D)成分が有する官能基と(F)成分が有する反応性基との組合せ等を考慮して選択すればよいが、例えば、樹脂組成物がマレイミド樹脂やエポキシ樹脂を含有する場合の硬化温度は、120乃至250℃が好ましく、硬化時間は概ね数十分間乃至数時間程度である。
The copper-clad laminate of the present invention can be obtained by heating the resin layer made of the resin composition provided on the surface of the copper foil to form a cured product (resin layer).
The curing temperature and curing time of the resin layer made of the resin composition may be selected in consideration of the combination of the functional group of the component (D) and the reactive group of the component (F). When the composition contains a maleimide resin or an epoxy resin, the curing temperature is preferably 120 to 250° C., and the curing time is approximately several tens of minutes to several hours.
尚、樹脂組成物からなる樹脂層の表面に、ポリイミドフィルムもしくはLCP(液晶ポリマー)等を積層させ、熱プレス後、加熱硬化することにより本発明の銅張積層体を備えた基材を得ることもできる。銅張積層体を備えた基材としては、例えば銅張積層板(CCL)、またはCCLの銅箔に回路パターンを有するプリント配線板や多層配線板等が挙げられる。 A base material having the copper-clad laminate of the present invention can be obtained by laminating a polyimide film or LCP (liquid crystal polymer) or the like on the surface of a resin layer made of a resin composition, followed by hot pressing and heat curing. can also Examples of the base material provided with a copper-clad laminate include copper-clad laminates (CCL), printed wiring boards and multilayer wiring boards having a circuit pattern on the copper foil of CCL.
以下、本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。実施例における「部」は質量部を、「%」は質量%を意味する。尚、実施例におけるGPCの測定条件は以下の通りである。
機種:TOSOH ECOSEC Elite HLC-8420GPC
カラム:TSKgel Super AWM-H
溶離液:NMP(N-メチルピロリドン);0.5ml/分、40℃
検出器:UV(示差屈折計)
分子量標準:ポリスチレン
EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. "Parts" in the examples means parts by mass, and "%" means % by mass. The GPC measurement conditions in the examples are as follows.
Model: TOSOH ECOSEC Elite HLC-8420GPC
Column: TSKgel Super AWM-H
Eluent: NMP (N-methylpyrrolidone); 0.5 ml/min, 40°C
Detector: UV (differential refractometer)
Molecular weight standard: polystyrene
合成例1((D)成分(ポリイミド樹脂1)の合成)
温度計、還流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び撹拌装置を取り付けた300mlの反応器に、DAPBAF(2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン4,4’-(ヘキサフルオロイソプロピリデン)ビス(2-アミノフェノール)(和歌山精化工業株式会社製、分子量366.26g/mol) 0.67部、PRIAMINE1075(クローダジャパン株式会社製、分子量539.52g/mol) 11.69部、BAFL(9,9-ビス(4-アミノフェニル)フルオレン、JFEケミカル株式会社製、分子量348.16g/mol) 5.89部、及びアニソール 68.24部を入れて70℃に加熱した。次いで、ODPA(オキシジフタル酸無水物、マナック株式会社製、分子量310.22g/mol) 12.41部、トリエチルアミン 0.81部及びトルエン 18.97部を加え、アミック酸の閉環に伴い生成した水をトルエンとの共沸で除去しながら130℃で8時間反応させてイミド化物(P)溶液(P-1)(フェノール性OH当量、7,953g/eq.、分子量99,300)を得た。続いて、カレンズMOI(昭和電工株式会社製、分子量155.15g/mol) 0.60部、重合禁止剤としてBHT(2,6-ジ-tert-ブチル-p-クレゾール) 0.08部を入れ、130℃で4時間反応させた後、残留するトリエチルアミンとトルエンを引き続き130℃で除去することによってポリイミド樹脂1溶液(ポリイミド1)を得た。
合成例1で用いたジアミン成分((a1)成分、(a2)成分及び(a3)成分)と酸無水物成分((B)成分)のモル比(ジアミン成分のモル数/酸無水物成分のモル数)は1.01、また、フェノール性水酸基と反応し得る官能基とエチレン性不飽和二重結合基を有する化合物(C)成分のモル数をMC、イミド化物(P)溶液(P-1)のフェノール性水酸基のモル数をMAB、イミド化物(P)溶液(P-1)の末端官能基のモル数をMPとすると、MC/(MAB+MP)=0.91であった。
Synthesis Example 1 (Synthesis of component (D) (polyimide resin 1))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4′-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.67 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 539 .52 g / mol) 11.69 parts, BAFL (9,9-bis (4-aminophenyl) fluorene, JFE Chemical Co., Ltd., molecular weight 348.16 g / mol) 5.89 parts, and anisole 68.24 parts and heated to 70° C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight of 310.22 g/mol), 0.81 parts of triethylamine and 18.97 parts of toluene were added, and the amic acid was added. The reaction was carried out at 130 ° C. for 8 hours while removing the water generated due to the ring closure by azeotrope with toluene. 99,300), followed by 0.60 parts of Karenz MOI (manufactured by Showa Denko KK, molecular weight: 155.15 g/mol), and BHT (2,6-di-tert-butyl-p- 0.08 part of cresol) was added and reacted at 130° C. for 4 hours, and then residual triethylamine and toluene were removed at 130° C. to obtain a polyimide resin 1 solution (polyimide 1).
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 1 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is MC, and the imide (P) solution (P- MC/(MAB+MP)=0.91, where MAB is the number of moles of phenolic hydroxyl groups in 1) and MP is the number of moles of terminal functional groups in the imide (P) solution (P-1).
合成例2((D)成分(ポリイミド樹脂2)の合成)
温度計、還流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び撹拌装置を取り付けた300mlの反応器に、DAPBAF(2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン4,4‘-(ヘキサフルオロイソプロピリデン)ビス(2-アミノフェノール)(和歌山精化工業株式会社製、分子量366.26g/mol) 0.70部、PRIAMINE1075(クローダジャパン株式会社製、分子量534.38g/mol) 11.22部、APB-N(1,3-ビス(3-アミノフェノキシ)ベンゼン、三井化学ファイン株式会社、分子量292.12g/mol) 5.16部、及びアニソール 65.66部を入れて70℃に加熱した。次いで、ODPA(オキシジフタル酸無水物、マナック株式会社製、分子量310.22g/mol) 12.41部、トリエチルアミン 0.81部及びトルエン 18.64部を加え、アミック酸の閉環に伴い生成した水をトルエンとの共沸で除去しながら130℃で8時間反応させてイミド化物(P)溶液(P-2)(フェノール性OH当量、7,302.3g/eq.、分子量101,200)を得た。続いて、カレンズMOI(昭和電工株式会社製、分子量155.15g/mol) 0.60部、重合禁止剤としてBHT(2,6-ジ-tert-ブチル-p-クレゾール) 0.09部を入れ、130℃で4時間反応させた後、残留するトリエチルアミンとトルエンを引き続き130℃で除去することによってポリイミド樹脂2溶液(ポリイミド2)を得た。
合成例2で用いたジアミン成分((a1)成分、(a2)成分及び(a3)成分)と酸無水物成分((B)成分)のモル比(ジアミン成分のモル数/酸無水物成分のモル数)は1.01、また、フェノール性水酸基と反応し得る官能基とエチレン性不飽和二重結合基を有する化合物(C)成分のモル数をMC、イミド化物(P)溶液(P-2)のフェノール性水酸基のモル数をMAB、イミド化物溶液(P-2)の末端官能基のモル数をMPとすると、MC/(MAB+MP)=0.90であった。
Synthesis Example 2 (Synthesis of component (D) (polyimide resin 2))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4'- (hexafluoroisopropylidene) bis (2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.70 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534 .38 g / mol) 11.22 parts, APB-N (1,3-bis (3-aminophenoxy) benzene, Mitsui Chemicals Fine Co., Ltd., molecular weight 292.12 g / mol) 5.16 parts, and anisole 65.66 parts and heated to 70° C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g/mol), 0.81 parts of triethylamine and 18.64 parts of toluene were added, The reaction was carried out at 130° C. for 8 hours while removing the water generated due to the ring closure of the amic acid by azeotropic distillation with toluene. eq., molecular weight 101,200), followed by 0.60 parts of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g/mol) and BHT (2,6-di-tert- 0.09 part of butyl-p-cresol) was added and reacted at 130° C. for 4 hours, and then residual triethylamine and toluene were removed at 130° C. to obtain a polyimide resin 2 solution (polyimide 2).
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 2 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is MC, and the imide (P) solution (P- MC/(MAB+MP)=0.90, where MAB is the number of moles of phenolic hydroxyl groups in 2) and MP is the number of moles of terminal functional groups in the imide solution (P-2).
合成例3((D)成分(ポリイミド樹脂3)の合成)
温度計、還流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び撹拌装置を取り付けた300mlの反応器に、DAPBAF(2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン4,4’-(ヘキサフルオロイソプロピリデン)ビス(2-アミノフェノール)(和歌山精化工業株式会社製、分子量366.26g/mol) 0.69部、PRIAMINE1075(クローダジャパン株式会社製、分子量534.38g/mol) 11.45部、APB-N(1,3-ビス(3-アミノフェノキシ)ベンゼン、三井化学ファイン株式会社、分子量292.12g/mol) 5.05部、及びアニソール 70.0部を入れて70℃に加熱した。次いで、BTDA(3,3’,4,4‘-ベンゾフェノンテトラカルボン酸二無水物、ダイセル株式会社製、分子量322.01g/mol) 12.88部、トリエチルアミン 0.81部及びトルエン 18.80部を加え、アミック酸の閉環に伴い生成した水をトルエンとの共沸で除去しながら130℃で8時間反応させイミド化物(P)溶液(P-3)(フェノール性OH当量、7,614.3g/eq.、分子量86,200)を得た。続いて、カレンズMOI(昭和電工株式会社製、分子量155.15g/mol) 0.60部、重合禁止剤としてBHT(2,6-ジ-tert-ブチル-p-クレゾール) 0.09部を入れ、130℃で4時間反応させた後、残留するトリエチルアミンとトルエンを引き続き10℃で除去することによってポリイミド樹脂3溶液(ポリイミド3)を得た。
合成例3で用いたジアミン成分((a1)成分、(a2)成分及び(a3)成分)と酸無水物成分((B)成分)のモル比(ジアミン成分のモル数/酸無水物成分のモル数)は1.01、また、フェノール性水酸基と反応し得る官能基とエチレン性不飽和二重結合基を有する化合物(C)成分のモル数をMC、イミド化物(P)溶液(P-3)のフェノール性水酸基のモル数をMAB、イミド化物(P)溶液(P-3)の末端官能基のモル数をMPとすると、MC/(MAB+MP)=0.90であった。
Synthesis Example 3 (Synthesis of component (D) (polyimide resin 3))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4'-(hexafluoroisopropylidene) bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.69 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534 .38 g / mol) 11.45 parts, APB-N (1,3-bis (3-aminophenoxy) benzene, Mitsui Chemicals Fine Co., Ltd., molecular weight 292.12 g / mol) 5.05 parts, and anisole 70.0 parts and heated to 70° C. Then, BTDA (3,3′,4,4′-benzophenonetetracarboxylic dianhydride, manufactured by Daicel Corporation, molecular weight 322.01 g/mol) 12.88 parts, triethylamine Add 0.81 part and 18.80 parts of toluene, and react at 130 ° C. for 8 hours while removing water generated due to ring closure of amic acid by azeotrope with toluene. Imidide (P) solution (P-3) (Phenolic OH equivalent, 7,614.3 g/eq., molecular weight 86,200) Subsequently, Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g/mol) 0.60 parts, polymerization prohibited 0.09 parts of BHT (2,6-di-tert-butyl-p-cresol) was added as an agent and reacted at 130° C. for 4 hours, followed by removal of residual triethylamine and toluene at 10° C. to produce a polyimide. A resin 3 solution (polyimide 3) was obtained.
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 3 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is MC, and the imide (P) solution (P- MC/(MAB+MP)=0.90, where MAB is the number of moles of phenolic hydroxyl groups in 3) and MP is the number of moles of terminal functional groups in the imide (P) solution (P-3).
合成例4((D)成分(ポリイミド樹脂4)の合成)
温度計、還流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び撹拌装置を取り付けた300mlの反応器に、DAPBAF(2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン4,4’-(ヘキサフルオロイソプロピリデン)ビス(2-アミノフェノール)(和歌山精化工業株式会社製、分子量366.26g/mol) 0.69部、PRIAMINE1075(クローダジャパン株式会社製、分子量534.38g/mol)11.92部、BAFL(9,9-ビス(4-アミノフェニル)フルオレン、JFEケミカル株式会社製、分子量348.16g/mol) 6.01部、及びアニソール 69.0部を入れて70℃に加熱した。次いで、ODPA(オキシジフタル酸無水物、マナック株式会社製、分子量310.22g/mol) 12.41部、トリエチルアミン 0.81部及びトルエン 19.08部を加え、アミック酸の閉環に伴い生成した水をトルエンとの共沸で除去しながら130℃で8時間反応させてイミド化物(P)溶液(P-4)(フェノール性OH当量、7,895g/eq.、分子量64,000)を得た。続いて、カレンズMOI(昭和電工株式会社製、分子量155.15g/mol) 0.58部、重合禁止剤としてBHT(2,6-ジ-tert-ブチル-p-クレゾール) 0.09部を入れ、130℃で4時間反応させた後、残留するトリエチルアミンとトルエンを引き続き130℃で除去することによってポリイミド樹脂4溶液(ポリイミド4)を得た。
合成例4で用いたジアミン成分((a1)成分、(a2)成分及び(a3)成分)と酸無水物成分((B)成分)のモル比(ジアミン成分のモル数/酸無水物成分のモル数)は1.01、また、フェノール性水酸基と反応し得る官能基とエチレン性不飽和二重結合基を有する化合物(C)成分のモル数をMC、イミド化物(P)溶液(P-4)のフェノール性水酸基のモル数をMAB、イミド化物(P)溶液(P-4)の末端官能基のモル数をMPとすると、MC/(MAB+MP)=0.85であった。
Synthesis Example 4 (Synthesis of component (D) (polyimide resin 4))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4'-(hexafluoroisopropylidene) bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.69 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534 .38 g / mol) 11.92 parts, BAFL (9,9-bis (4-aminophenyl) fluorene, JFE Chemical Co., Ltd., molecular weight 348.16 g / mol) 6.01 parts, and anisole 69.0 parts and heated to 70° C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight of 310.22 g/mol), 0.81 parts of triethylamine and 19.08 parts of toluene were added, and the amic acid was added. The reaction was carried out at 130 ° C. for 8 hours while removing the water generated due to the ring closure by azeotrope with toluene, and the imidide (P) solution (P-4) (phenolic OH equivalent, 7,895 g / eq., molecular weight Subsequently, 0.58 parts of Karenz MOI (manufactured by Showa Denko KK, molecular weight 155.15 g/mol) and BHT (2,6-di-tert-butyl-p- 0.09 part of cresol) was added and reacted at 130° C. for 4 hours, and then residual triethylamine and toluene were removed at 130° C. to obtain a polyimide resin 4 solution (polyimide 4).
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 4 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is MC, and the imide (P) solution (P- MC/(MAB+MP)=0.85, where MAB is the number of moles of phenolic hydroxyl groups in 4) and MP is the number of moles of terminal functional groups in the imide (P) solution (P-4).
合成例5((D)成分(比較用ポリイミド樹脂1)の合成)
温度計、還流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び撹拌装置を取り付けた300mlの反応器に、DAPBAF(2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン4,4’-(ヘキサフルオロイソプロピリデン)ビス(2-アミノフェノール)(和歌山精化工業株式会社製、分子量366.26g/mol) 0.67部、PRIAMINE1075(クローダジャパン株式会社製、分子量539.52g/mol) 11.69部、BAFL(9,9-ビス(4-アミノフェニル)フルオレン、JFEケミカル株式会社製、分子量348.16g/mol) 5.89部、及びアニソール 68.24部を入れて70℃に加熱した。次いで、ODPA(オキシジフタル酸無水物、マナック株式会社製、分子量310.22g/mol) 12.41部、トリエチルアミン 0.81部及びトルエン 18.97部を加え、アミック酸の閉環に伴い生成した水をトルエンとの共沸で除去しながら130℃で8時間反応させて比較用ポリイミド樹脂1溶液(比較用ポリイミド1)(フェノール性OH当量、7,953g/eq.、分子量99,300)を得た。
合成例5で用いたジアミン成分((a1)成分、(a2)成分及び(a3)成分)と酸無水物成分((B)成分)のモル比(ジアミン成分のモル数/酸無水物成分のモル数)は1.01であった。
Synthesis Example 5 (Synthesis of component (D) (comparative polyimide resin 1))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4′-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.67 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 539 .52 g / mol) 11.69 parts, BAFL (9,9-bis (4-aminophenyl) fluorene, JFE Chemical Co., Ltd., molecular weight 348.16 g / mol) 5.89 parts, and anisole 68.24 parts and heated to 70° C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight of 310.22 g/mol), 0.81 parts of triethylamine and 18.97 parts of toluene were added, and the amic acid was added. While removing the water generated due to the ring closure by azeotrope with toluene, the reaction was performed at 130 ° C. for 8 hours to give a solution of comparative polyimide resin 1 (comparative polyimide 1) (phenolic OH equivalent, 7,953 g / eq., A molecular weight of 99,300) was obtained.
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 5 (moles of diamine component / number of acid anhydride components number of moles) was 1.01.
合成例6((D)成分(比較用ポリイミド樹脂2)の合成)
温度計、還流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び撹拌装置を取り付けた300mlの反応器に、PRIAMINE1075(クローダジャパン株式会社製、分子量534.38g/mol) 11.38部、BAFL(9,9-ビス(4-アミノフェニル)フルオレン、JFEケミカル株式会社製、分子量348.16g/mol) 5.64部、及びアニソール 170.06部を入れて70℃に加熱した。次いで、ODPA(オキシジフタル酸無水物、マナック株式会社製、分子量310.22g/mol) 12.88部、トリエチルアミン 0.81部及びトルエン 18.75部を加え、アミック酸の閉環に伴い生成した水をトルエンとの共沸で除去しながら130℃で8時間反応させた後、残留するトリエチルアミンとトルエンを引き続き130℃で除去することによって比較用ポリイミド樹脂2溶液(比較用ポリイミド2)(分子量89,400)を得た。合成例6で用いたジアミン成分((a1)成分、(a2)成分及び(a3)成分)と酸無水物成分((B)成分)のモル比(ジアミン成分のモル数/酸無水物成分のモル数)は1.01であった。
Synthesis Example 6 (Synthesis of component (D) (comparative polyimide resin 2))
11.38 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol) was added to a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen introduction device and a stirring device. , BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Co., Ltd., molecular weight 348.16 g/mol) and 170.06 parts of anisole were added and heated to 70°C. Next, 12.88 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g/mol), 0.81 part of triethylamine and 18.75 parts of toluene are added, and the water generated due to ring closure of amic acid is removed. After reaction at 130° C. for 8 hours with azeotropic removal with toluene, residual triethylamine and toluene were subsequently removed at 130° C. to give a solution of Comparative Polyimide Resin 2 (Comparative Polyimide 2) (molecular weight 89,400). ). The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 6 (moles of diamine component / number of acid anhydride components number of moles) was 1.01.
合成例7((D)成分(比較用ポリイミド樹脂3)の合成)
温度計、還流冷却器、ディーンスターク装置、粉体導入口、窒素導入装置及び撹拌装置を取り付けた300mlの反応器に、DAPBAF(2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン4,4‘-(ヘキサフルオロイソプロピリデン)ビス(2-アミノフェノール)(和歌山精化工業株式会社製、分子量366.26g/mol) 6.60部、PRIAMINE1075(クローダジャパン株式会社製、分子量534.38g/mol) 12.07部、及びアニソール 70.20部を入れて70℃に加熱した。次いで、ODPA(オキシジフタル酸無水物、マナック株式会社製、分子量310.22g/mol) 12.88部、トリエチルアミン 0.81部及びトルエン 19.23部を加え、アミック酸の閉環に伴い生成した水をトルエンとの共沸で除去しながら130℃で8時間反応させてイミド化物(P)溶液(P-7)(フェノール性OH当量、835g/eq.、分子量32,200)を得た。 続いて、カレンズMOI(昭和電工株式会社製、分子量155.15g/mol) 5.96部、重合禁止剤としてBHT(2,6-ジ-tert-ブチル-p-クレゾール) 1.0部を入れ、130℃で4時間反応させた後、残留するトリエチルアミンとトルエンを引き続き130℃で除去することによって比較用ポリイミド樹脂3溶液(比較用ポリイミド3)を得た。
合成例7で用いたジアミン成分((a1)成分、(a2)成分及び(a3)成分)と酸無水物成分((B)成分)のモル比(ジアミン成分のモル数/酸無水物成分のモル数)は1.01、また、フェノール性水酸基と反応し得る官能基とエチレン性不飽和二重結合基を有する化合物(C)成分のモル数をMC、イミド化物(P)溶液(P-7)のフェノール性水酸基のモル数をMAB、イミド化物(P)溶液(P-7)の末端官能基のモル数をMPとすると、MC/(MAB+MP)=0.55であった。
Synthesis Example 7 (Synthesis of component (D) (comparative polyimide resin 3))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4′-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 6.60 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534 .38 g/mol) and 70.20 parts of anisole were added and heated to 70° C. Then, 12.88 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., molecular weight: 310.22 g/mol). , 0.81 parts of triethylamine and 19.23 parts of toluene were added, and the reaction was carried out at 130 ° C. for 8 hours while removing the water generated due to the ring closure of the amic acid by azeotrope with toluene. -7) (phenolic OH equivalent, 835 g / eq., molecular weight 32,200) was obtained.Next, Karenz MOI (manufactured by Showa Denko KK, molecular weight 155.15 g / mol) 5.96 parts, polymerization inhibitor 1.0 parts of BHT (2,6-di-tert-butyl-p-cresol) was added as a solution and reacted at 130°C for 4 hours. A polyimide resin 3 solution (comparative polyimide 3) was obtained.
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 7 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is MC, and the imide (P) solution (P- MC/(MAB+MP)=0.55, where MAB is the number of moles of phenolic hydroxyl groups in 7) and MP is the number of moles of terminal functional groups in the imide (P) solution (P-7).
配合例1乃至30(樹脂組成物の調整(配合例1乃至20は本発明の樹脂付き銅箔用の樹脂組成物、配合例21乃至30は比較例の樹脂付き銅箔用の樹脂組成物)
表1乃至3に示した配合量(単位は「部」、表中の部数は、溶剤を含まない固形分換算の部数である)で各成分を配合した後、固形分濃度が20質量%となる量のアニソールを溶剤として追加して均一に混合することにより、樹脂付き銅箔の樹脂層となる樹脂組成物をそれぞれ調整した。
Formulation Examples 1 to 30 (Adjustment of resin composition (Formulation Examples 1 to 20 are resin compositions for resin-coated copper foils of the present invention, Formulation Examples 21 to 30 are resin compositions for resin-coated copper foils of comparative examples)
After blending each component in the blending amount shown in Tables 1 to 3 (unit is "part", the number of parts in the table is the number of parts converted to solid content without solvent), the solid content concentration is 20% by mass. By adding an appropriate amount of anisole as a solvent and uniformly mixing, each resin composition that will be the resin layer of the resin-coated copper foil was prepared.
表1乃至3における各成分は以下の通りである。尚、無機充填剤の比表面積はBET法で測定した値である。
<ポリイミド樹脂>
(D-1)乃至(D-4);合成例1乃至4で得られたポリイミド1乃至4
(D-5)乃至(D-7);合成例5乃至7で得られた比較用ポリイミド1乃至3
<熱硬化性樹脂>
MIR-3000-70MT;マレイミド樹脂、日本化薬(株)製
XD-1000;エポキシ樹脂、日本化薬(株)製
ZXR-1889H;エポキシアクリレート樹脂、日本化薬(株)製
<無機充填剤>
(E-1);SFP-30M(デンカ株式会社製、溶融シリカ、平均粒子径0.6μm、比表面積6.2m2/g)
(E-2);SFP-20M(デンカ株式会社製、溶融シリカ、平均粒子径0.4μm、比表面積11.2m2/g)
(E-3);FB-3SDC(デンカ株式会社製、溶融シリカ、平均粒子径3.1μm、比表面積3.6m2/g)
(E-4);Sciqas0.7μm(堺化学工業株式会社製、溶融シリカ、平均粒子径0.7μm、比表面積4.3m2/g)
(E-5)BA-1(日記触媒化成株式会社製、中空シリカ、平均粒子径16μm、比表面積2.0m2/g)
(E-6);Sciqas0.7μm(堺化学工業株式会社製、表面エポキシシラン処理溶融シリカ、平均粒子径0.7μm、比表面積4.3m2/g)
(E-7);Sciqas0.7μm(堺化学工業株式会社製、表面ポリシロキサン処理溶融シリカ、平均粒子径0.7μm、比表面積4.3m2/g)
(E-8);10SX-CH1(株式会社アドマテックス製、表面アミノシラン処理溶融シリカ、5μm粗粒カット後平均粒子径1.1μm、比表面積15m2/g)
(E-9);Sciqas0.1μm(堺化学工業株式会社製、溶融シリカ、平均粒子径0.1μm、比表面積21.5m2/g)
(E-10);ナノエースD600(日本タルク株式会社製、タルク、平均粒子径0.6μm、比表面積24m2/g)
(E-11);DAW-03(デンカ株式会社製、アルミナ、平均粒子径4.9μm、比表面積0.5m2/g)
<硬化剤>
DCP;ジクミルパーオキシド、化薬ヌーリオン(株)製
<添加剤>
KR-513;シランカップリング剤、信越化学(株)製
TT-LX;潤滑油添加剤、城北化学(株)製
KTL-8FH;テフロン(登録商標)パウダー、平均粒子径3.5μm、株式会社喜多村製
Each component in Tables 1 to 3 is as follows. Incidentally, the specific surface area of the inorganic filler is a value measured by the BET method.
<Polyimide resin>
(D-1) to (D-4); Polyimides 1 to 4 obtained in Synthesis Examples 1 to 4
(D-5) to (D-7); Comparative polyimides 1 to 3 obtained in Synthesis Examples 5 to 7
<Thermosetting resin>
MIR-3000-70MT; Maleimide resin, Nippon Kayaku Co., Ltd. XD-1000; Epoxy resin, Nippon Kayaku Co., Ltd. ZXR-1889H; Epoxy acrylate resin, Nippon Kayaku Co., Ltd. <Inorganic filler>
(E-1); SFP-30M (manufactured by Denka Co., Ltd., fused silica, average particle size 0.6 μm, specific surface area 6.2 m 2 /g)
(E-2); SFP-20M (manufactured by Denka Co., Ltd., fused silica, average particle size 0.4 μm, specific surface area 11.2 m 2 /g)
(E-3); FB-3SDC (manufactured by Denka Co., Ltd., fused silica, average particle size 3.1 μm, specific surface area 3.6 m 2 /g)
(E-4); Sciqas 0.7 μm (manufactured by Sakai Chemical Industry Co., Ltd., fused silica, average particle size 0.7 μm, specific surface area 4.3 m 2 /g)
(E-5) BA-1 (manufactured by Nikki Shokubai Kasei Co., Ltd., hollow silica, average particle diameter 16 μm, specific surface area 2.0 m 2 /g)
(E-6); Sciqas 0.7 μm (manufactured by Sakai Chemical Industry Co., Ltd., surface epoxysilane-treated fused silica, average particle size 0.7 μm, specific surface area 4.3 m 2 /g)
(E-7); Sciqas 0.7 μm (manufactured by Sakai Chemical Industry Co., Ltd., surface polysiloxane-treated fused silica, average particle size 0.7 μm, specific surface area 4.3 m 2 /g)
(E-8); 10SX-CH1 (manufactured by Admatechs Co., Ltd., surface aminosilane-treated fused silica, average particle size after cutting 5 μm coarse particles: 1.1 μm, specific surface area: 15 m 2 /g)
(E-9); Sciqas 0.1 μm (manufactured by Sakai Chemical Industry Co., Ltd., fused silica, average particle size 0.1 μm, specific surface area 21.5 m 2 /g)
(E-10); Nanoace D600 (manufactured by Nippon Talc Co., Ltd., talc, average particle size 0.6 μm, specific surface area 24 m 2 /g)
(E-11); DAW-03 (manufactured by Denka Co., Ltd., alumina, average particle size 4.9 μm, specific surface area 0.5 m 2 /g)
<Curing agent>
DCP; dicumyl peroxide, manufactured by Kayaku Nourion Co., Ltd. <Additive>
KR-513; Silane coupling agent, Shin-Etsu Chemical Co., Ltd. TT-LX; Lubricating oil additive, Johoku Chemical Co., Ltd. KTL-8FH; Teflon (registered trademark) powder, average particle size 3.5 μm, Co., Ltd. Made in Kitamura
実施例1乃至20及び比較例1乃至10(本発明及び比較例の樹脂付き銅箔の作製)
福田金属箔粉工業株式会社製の超低粗度無粗化処理電解銅箔CF-T9DA-SV(以下、「T9DA」と記載する。銅箔の厚さ12μm、表面粗さ0.85μm。)の粗面に、オートマチックアプリケータを用いて、塗布、乾燥後の樹脂層の膜厚が30μmとなる量の配合例1乃至20の樹脂組成物をそれぞれ塗布し、120℃で10分間加熱乾燥して実施例1乃至20の樹脂付き銅箔を作成した。また、配合例21乃至30の樹脂組成物を用いて、前記と同じ方法で比較例1乃至10の樹脂付き銅箔を作製した。
Examples 1 to 20 and Comparative Examples 1 to 10 (Preparation of resin-coated copper foils of the present invention and comparative examples)
Fukuda Metal Foil & Powder Co., Ltd. ultra-low roughness non-roughening treated electrolytic copper foil CF-T9DA-SV (hereinafter referred to as “T9DA”. Copper foil thickness 12 μm, surface roughness 0.85 μm.) Using an automatic applicator, each of the resin compositions of Formulation Examples 1 to 20 was applied to the rough surface of , and dried by heating at 120 ° C. for 10 minutes. The resin-coated copper foils of Examples 1 to 20 were prepared. Further, using the resin compositions of Formulation Examples 21 to 30, resin-coated copper foils of Comparative Examples 1 to 10 were produced in the same manner as described above.
(樹脂付き銅箔の有する樹脂層の膜厚のばらつき評価)
実施例1乃至20及び比較例1乃至10で得られた樹脂付き銅箔について、任意で選んだ10ヶ所の厚さの測定値から銅箔の厚さ除して、樹脂層の10ヶ所の膜厚を求めた。前記で求めた10ヶ所の膜厚のうち、最大の膜厚と最小の膜厚の差を算出し、下記の評価基準で膜厚のばらつきを評価した。結果を表1乃至3に示した。
〇・・・最大の膜厚と最小値の膜厚の差が4.0μm未満
×・・・最大の膜厚と最小値の膜厚の差が4.0μm以上
(Evaluation of variation in film thickness of resin layer possessed by resin-coated copper foil)
For the resin-coated copper foils obtained in Examples 1 to 20 and Comparative Examples 1 to 10, the thickness of the copper foil is divided from the thickness measurement values at 10 arbitrarily selected locations, and the thickness of the resin layer is obtained at 10 locations. I asked for the thickness. Among the 10 film thicknesses obtained above, the difference between the maximum film thickness and the minimum film thickness was calculated, and the variation in film thickness was evaluated according to the following evaluation criteria. The results are shown in Tables 1-3.
○: The difference between the maximum film thickness and the minimum film thickness is less than 4.0 μm ×: The difference between the maximum film thickness and the minimum film thickness is 4.0 μm or more
実施例21乃至40及び比較例11乃至20(本発明及び比較例の銅張積層体の作製)
実施例1乃至20及び比較例1乃至10で得られた樹脂付き銅箔の樹脂層にPPEプリプレグ(Meteorwave4000、AGC nelco(株)製)を重ね合わせ、200℃で60分間、3MPaの条件で真空プレスして樹脂層を硬化させることにより実施例21乃至40及び比較例11乃至20の銅張積層体をそれぞれ作成した。
Examples 21 to 40 and Comparative Examples 11 to 20 (Production of copper-clad laminates of the present invention and comparative examples)
PPE prepreg (Meteorwave 4000, manufactured by AGC nelco Co., Ltd.) was superimposed on the resin layer of the resin-coated copper foil obtained in Examples 1 to 20 and Comparative Examples 1 to 10, and vacuum was applied at 200 ° C. for 60 minutes at 3 MPa. Copper-clad laminates of Examples 21 to 40 and Comparative Examples 11 to 20 were produced by pressing to cure the resin layers.
(銅張積層体の接着強度の評価)
実施例21乃至40及び比較例11乃至20で得られた各銅張積層体を10mm幅に切り出し、オートグラフAGS-X-500N(株式会社島津製作所製)を用いて、PPEプリプレグと樹脂組成物の硬化物からなる樹脂層を有する銅箔との間の90°引きはがし強さ(引き剥がし速度は50mm/min)を測定し、下記の評価基準で接着強度を評価した。尚、試験後のサンプルを目視で確認したところ、全て凝集破壊が起こっていた。結果を表1乃至3に示した。
◎・・・6.5N/cm以上
〇・・・5.5N/cm以上6.5N/cm未満
△・・・4.5N/cm以上5.5N/cm未満
×・・・4.5N/cm未満
(Evaluation of adhesive strength of copper-clad laminate)
Each copper-clad laminate obtained in Examples 21 to 40 and Comparative Examples 11 to 20 was cut into 10 mm widths, and PPE prepregs and resin compositions were prepared using Autograph AGS-X-500N (manufactured by Shimadzu Corporation). 90° peeling strength (peeling speed: 50 mm/min) between a copper foil having a resin layer composed of a cured product of (1) was measured, and the adhesive strength was evaluated according to the following evaluation criteria. Incidentally, when the samples after the test were visually checked, cohesive failure had occurred in all of them. The results are shown in Tables 1-3.
◎: 6.5 N/cm or more ○: 5.5 N/cm or more and less than 6.5 N/cm △: 4.5 N/cm or more and less than 5.5 N/cm ×: 4.5 N/cm less than cm
(銅張積層体の熱特性の評価)
実施例1乃至20及び比較例1乃至10で得られた樹脂付き銅箔を、POT-200C(太洋電機産業株式会社製)で288℃に熱したハンダ浴にフロートさせ、フクレが出るまでの時間を測定し、下記の評価基準で熱特性を評価した。結果を表1乃至3に示した。
◎・・・10分以上膨れなし
〇・・・1分以上10分未満で膨れ発生
×・・・1分未満で膨れ発生
(Evaluation of thermal properties of copper clad laminate)
The resin-coated copper foils obtained in Examples 1 to 20 and Comparative Examples 1 to 10 were floated in a solder bath heated to 288 ° C. with POT-200C (manufactured by Taiyo Denki Sangyo Co., Ltd.) until blisters appeared. The time was measured and the thermal properties were evaluated according to the following evaluation criteria. The results are shown in Tables 1-3.
◎: No swelling for 10 minutes or more ○: Blistering occurred for 1 minute or more and less than 10 minutes ×: Blistering occurred for less than 1 minute
(樹脂組成物の硬化物からなる樹脂層の誘電率及び誘電正接の評価)
配合例1乃至30の樹脂組成物の塗布量を、樹脂層の膜厚が30μmとなる量から100μmとなる量に変更した以外は実施例1乃至20及び比較例1乃至10と同じ方法で樹脂付き銅箔を作製した後、200℃で60分間加熱して樹脂層を硬化させて銅張積層体をそれぞれ得た。前記で得られた銅張積層体の銅箔を、液比重45ボーメ度の塩化鉄(III)溶液でエッチングして除去し、イオン交換水で洗浄後、105℃で10分間乾燥することにより樹脂組成物の硬化物からなる樹脂層をそれぞれ得た。前記で得られた樹脂層について、オートグラフAGS-X-500N(株式会社島津製作所製)を用いて破断点応力、破断点伸度、弾性率を、またネットワークアナライザー8719ET(アジレントテクノロジー製)を用いて空洞共振法によって10GHzにおける誘電率及び誘電正接を測定した。結果を表1乃至3に示した。
(Evaluation of Dielectric Constant and Dielectric Loss Tangent of Resin Layer Consisting of Cured Resin Composition)
Resins were prepared in the same manner as in Examples 1 to 20 and Comparative Examples 1 to 10, except that the coating amount of the resin composition of Formulation Examples 1 to 30 was changed from an amount that resulted in a film thickness of the resin layer of 30 µm to an amount that resulted in a film thickness of 100 µm. After the coated copper foil was produced, the resin layer was cured by heating at 200° C. for 60 minutes to obtain a copper-clad laminate. The copper foil of the copper clad laminate obtained above is removed by etching with an iron (III) chloride solution having a liquid specific gravity of 45 Baume degrees, washed with ion-exchanged water, and dried at 105 ° C. for 10 minutes to obtain a resin. A resin layer composed of a cured product of the composition was obtained. For the resin layer obtained above, the stress at break, elongation at break, and elastic modulus were measured using Autograph AGS-X-500N (manufactured by Shimadzu Corporation), and using a network analyzer 8719ET (manufactured by Agilent Technologies). The dielectric constant and dielectric loss tangent at 10 GHz were measured by the cavity resonance method. The results are shown in Tables 1-3.
表1乃至3の結果より、本発明の樹脂付き銅箔は膜厚のばらつきが少なく、また樹脂付き銅箔の有する樹脂組成物からなる樹脂層を硬化させて得られる銅張積層体は接着強度及び耐熱性が高く、更に樹脂組成物からなる樹脂層の硬化物は誘電特性に優れていることは明らかである。 From the results in Tables 1 to 3, the resin-coated copper foil of the present invention has little variation in film thickness, and the copper-clad laminate obtained by curing the resin layer composed of the resin composition of the resin-coated copper foil has an adhesive strength. and high heat resistance, and it is clear that the cured product of the resin layer made of the resin composition is excellent in dielectric properties.
本発明の樹脂付き銅箔の有する樹脂層となる樹脂組成物は塗工性に優れるため、容易な方法で樹脂付き銅箔を調製することが出来る。また、本発明の樹脂付き銅箔の有する樹脂組成物からなる樹脂層を硬化させていられる銅張積層体は、樹脂層の硬化物と銅箔との接着性に優れ、樹脂層の硬化物の耐熱性が良好であると共に、誘電特性に優れるため、プリント配線板等に好適に用いることができる。
Since the resin composition that forms the resin layer of the resin-coated copper foil of the present invention has excellent coatability, the resin-coated copper foil can be prepared by a simple method. In addition, the copper-clad laminate obtained by curing the resin layer composed of the resin composition of the resin-coated copper foil of the present invention has excellent adhesion between the cured resin layer and the copper foil, and the cured resin layer has excellent adhesion. Since it has good heat resistance and excellent dielectric properties, it can be suitably used for printed wiring boards and the like.
Claims (10)
で表される化合物を含む請求項1に記載の樹脂付き銅箔。 An aminophenol compound (a1) having at least two amino groups in one molecule is represented by the following formula (1)
The resin-coated copper foil according to claim 1, comprising a compound represented by.
からなる群より選択される化合物を含む請求項1に記載の樹脂付き銅箔。 Tetrabasic dianhydride (B) is represented by the following formulas (3) to (11)
The resin-coated copper foil according to claim 1, comprising a compound selected from the group consisting of
カルボン酸クロリド基である請求項1に記載の樹脂付き銅箔。 The functional group capable of reacting with the phenolic hydroxyl group of the compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is an isocyanate group or a carboxylic acid chloride group. Resin-coated copper foil as described.
A copper-clad laminate obtained by curing a resin layer composed of a resin composition contained in the resin-coated copper foil according to any one of claims 1 to 9.
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