WO2020080352A1 - 樹脂組成物、硬化膜、硬化膜付きプリント配線板およびその製造方法 - Google Patents
樹脂組成物、硬化膜、硬化膜付きプリント配線板およびその製造方法 Download PDFInfo
- Publication number
- WO2020080352A1 WO2020080352A1 PCT/JP2019/040438 JP2019040438W WO2020080352A1 WO 2020080352 A1 WO2020080352 A1 WO 2020080352A1 JP 2019040438 W JP2019040438 W JP 2019040438W WO 2020080352 A1 WO2020080352 A1 WO 2020080352A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- resin
- group
- cured film
- wiring board
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims 3
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000011347 resin Substances 0.000 claims abstract description 72
- 239000003063 flame retardant Substances 0.000 claims abstract description 57
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011230 binding agent Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 125000001424 substituent group Chemical group 0.000 claims abstract description 24
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims abstract description 8
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 8
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 15
- 239000003086 colorant Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 238000001723 curing Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000016 photochemical curing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 48
- -1 diphosphonate compound Chemical class 0.000 description 41
- 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 19
- 238000011161 development Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 150000002009 diols Chemical class 0.000 description 16
- 229920001721 polyimide Polymers 0.000 description 16
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- JRRDISHSXWGFRF-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOC JRRDISHSXWGFRF-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000000038 blue colorant Substances 0.000 description 3
- 239000001055 blue pigment Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000001053 orange pigment Substances 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000001057 purple pigment Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 125000003003 spiro group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 2
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 2
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-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
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 2
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 239000001061 orange colorant Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OTOIIPJYVQJATP-UHFFFAOYSA-N pantoic acid Chemical compound OCC(C)(C)C(O)C(O)=O OTOIIPJYVQJATP-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- ASFFINXMVZLDKE-UHFFFAOYSA-N 1-(1,3,5-triazinan-1-yl)prop-2-en-1-one Chemical compound C=CC(=O)N1CNCNC1 ASFFINXMVZLDKE-UHFFFAOYSA-N 0.000 description 1
- ZLDFIWDSBWFSMK-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]-2-methoxyethane;1-methoxy-2-[2-(2-methoxyethoxy)ethoxy]ethane Chemical compound COCCOCCOCCOC.CCOCCOCCOCCOC ZLDFIWDSBWFSMK-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical class CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- DGADNPLBVRLJGD-UHFFFAOYSA-N 2,3-dihydroxy-2-methylpropanoic acid Chemical compound OCC(O)(C)C(O)=O DGADNPLBVRLJGD-UHFFFAOYSA-N 0.000 description 1
- 229940082044 2,3-dihydroxybenzoic acid Drugs 0.000 description 1
- LOUGYXZSURQALL-UHFFFAOYSA-N 2,3-dihydroxybutanoic acid Chemical compound CC(O)C(O)C(O)=O LOUGYXZSURQALL-UHFFFAOYSA-N 0.000 description 1
- KTHRQDFQEQQGDF-UHFFFAOYSA-N 2,3-dihydroxyhexadecanoic acid Chemical compound CCCCCCCCCCCCCC(O)C(O)C(O)=O KTHRQDFQEQQGDF-UHFFFAOYSA-N 0.000 description 1
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- QUPKCFBHJFNUEW-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCCN1 QUPKCFBHJFNUEW-UHFFFAOYSA-N 0.000 description 1
- IPJGPNZOIMZKEK-UHFFFAOYSA-N 2-ethyl-4-hydroxy-2-(2-hydroxyethyl)butanoic acid Chemical compound OCCC(CC)(CCO)C(O)=O IPJGPNZOIMZKEK-UHFFFAOYSA-N 0.000 description 1
- YRCGEXZERNXCNP-UHFFFAOYSA-N 2-ethyl-5-hydroxypentanoic acid Chemical compound CCC(C(O)=O)CCCO YRCGEXZERNXCNP-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical class OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- BTYIFQSAIPDZQW-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole Chemical compound CC(C)C1=NCCN1 BTYIFQSAIPDZQW-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- FQHUDZKKDCTQET-UHFFFAOYSA-N 2-undecyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCC1=NCCN1 FQHUDZKKDCTQET-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- DNFUJUFGVPNZMP-UHFFFAOYSA-N 4-hydroxy-2-(2-hydroxyethyl)-2-methylbutanoic acid Chemical compound OCCC(C)(CCO)C(O)=O DNFUJUFGVPNZMP-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IDIMQYQWJLCKLC-UHFFFAOYSA-N 5-hydroxy-2-(3-hydroxypropyl)-2-methylpentanoic acid Chemical compound OCCCC(C)(CCCO)C(O)=O IDIMQYQWJLCKLC-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- JJUVAPMVTXLLFR-UHFFFAOYSA-N 5-methyl-2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1C(C)CN=C1C1=CC=CC=C1 JJUVAPMVTXLLFR-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 description 1
- 150000003869 acetamides Chemical class 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical class C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 229940114055 beta-resorcylic acid Drugs 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- RMWQBWIPOMZVKK-UHFFFAOYSA-N n-[(4-hydroxy-3,5-dimethylphenyl)methyl]prop-2-enamide Chemical compound CC1=CC(CNC(=O)C=C)=CC(C)=C1O RMWQBWIPOMZVKK-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000343 polyazomethine Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Chemical class 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000001062 red colorant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- CPOUUWYFNYIYLQ-UHFFFAOYSA-M tetra(propan-2-yl)azanium;hydroxide Chemical compound [OH-].CC(C)[N+](C(C)C)(C(C)C)C(C)C CPOUUWYFNYIYLQ-UHFFFAOYSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- DIHAURBCYGTGCV-UHFFFAOYSA-N xi-4,5-Dihydro-2,4(5)-dimethyl-1H-imidazole Chemical compound CC1CN=C(C)N1 DIHAURBCYGTGCV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Definitions
- the present invention relates to a resin composition, a cured film obtained by curing the resin composition, and a printed wiring board provided with the cured film.
- An insulating cured film is formed on the circuit of the printed wiring board using an insulating thermosetting resin or an ultraviolet curable resin in order to maintain insulation reliability.
- the insulating cured film may be required to have flame retardancy, and a non-halogen flame retardant is used from the viewpoint of environmental load (Patent Document 1).
- An object of the present invention is to provide a cured film having excellent flame retardancy, less likely to cause defects such as bleed-out, and excellent in flexibility, and a resin composition used for forming the cured film.
- the resin composition of the present invention contains (a) a binder resin, (b) a thermosetting resin, and (c) a flame retardant.
- the binder resin (a) is a polymer having a urethane bond in the molecule, and may further have a carboxy group and / or a photopolymerizable functional group.
- the acid value of the binder resin may be 5 to 200 mgKOH / g.
- the (b) thermosetting resin is, for example, a polyfunctional epoxy resin.
- the flame retardant is an organic phosphorus compound (spiro ring diphosphonate compound) represented by the following general formula.
- R 2 and R 5 are each independently a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or an anthryl group which may have a substituent.
- R 1 , R 3 , R 4 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent or a naphthyl group which may have a substituent. , Or an anthryl group which may have a substituent.
- the resin composition comprises, in addition to the components (a), (b) and (c), (d) a compound having an ethylenically unsaturated group (photocurable compound), (e) a photopolymerization initiator, (F) A colorant or the like may be included.
- the content of the component (c) in the resin composition may be about 10 to 30 parts by weight based on 100 parts by weight of the total solid content.
- a coating film (insulating film) is formed by applying the above resin composition on a substrate and drying the solvent as necessary.
- a cured film is obtained by photo-curing and / or heat-curing this insulating film.
- the above resin composition is applied to the surface of a printed wiring board to form a coating film, and at least a part of the surface of the coating film is irradiated with an actinic ray to perform photo-curing, and if necessary, alkali After development by the like, the coating film after photo-curing is heated and thermally cured to form a printed wiring board with a cured film.
- the printed wiring board may be a flexible printed wiring board using a flexible film substrate such as a polyimide film.
- the cured film formed from the above resin composition has excellent flame retardancy, is less likely to cause defects such as bleed-out of the flame retardant, and is also excellent in flexibility.
- the resin composition of the present invention contains (a) a binder resin, (b) a thermosetting resin, and (c) an organophosphorus compound. Since it has a thermosetting resin, the resin composition has thermosetting properties.
- the binder resin (a) may be one having reactivity with the thermosetting resin.
- the binder resin may have a photocurable functional group such as an ethylenically unsaturated group. Since the resin composition contains the binder resin having photocurability, the resin composition has photocurability (photosensitivity) in addition to thermosetting.
- the resin composition may further contain (d) a compound having an ethylenically unsaturated group (photocurable compound).
- the resin composition may further contain (e) a photopolymerization initiator.
- the resin composition may further contain (f) a colorant.
- a colorant By containing the colorant, the insulating film obtained from the resin composition can be arbitrarily colored.
- the binder resin is a polymer that is soluble in an organic solvent and has a polyethylene glycol-equivalent weight average molecular weight of 1,000 or more and 1,000,000 or less.
- the weight average molecular weight of the binder resin is more preferably 2,000 to 200,000, further preferably 3,000 to 100,000, particularly preferably 4,000 to 50,000.
- the weight average molecular weight of the binder resin is within the above range, a cured film having excellent heat resistance and flexibility can be easily obtained.
- the binder resin is a urethane polymer having at least one urethane bond in the molecule.
- the urethane polymer is obtained, for example, by reacting a diol with a diisocyanate.
- the diisocyanate compound may be either an alicyclic diisocyanate compound or an aliphatic diisocyanate compound.
- the diisocyanate compound may be a reaction product of a compound having two or more functional groups capable of reacting with an isocyanate group, and may be, for example, a urethane compound having an isocyanate group at a terminal.
- the diisocyanate compound may be any of aromatic isocyanate, alicyclic isocyanate, aliphatic isocyanate and alicyclic diisocyanate.
- the diisocyanate compound may be a reaction product of a compound having two or more functional groups capable of reacting with the isocyanate group of the diisocyanate compound, and may be, for example, a urethane compound having an isocyanate group at the terminal.
- a urethane compound having an isocyanate group at the terminal.
- Examples of the alicyclic diisocyanate include hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate and norbornene diisocyanate.
- Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and the like.
- diol examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1, 6-hexanediol, 1,8-octanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol
- Polyoxyalkylene diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymers of tetramethylene glycol and neopentyl glycol; polyhydric alcohols and polybasic acids Polyester diol obtained: Polycarbonate diol having a carbonate
- Two or more diols may be used in combination.
- a long-chain diol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyalkylene diol, polyester diol, polycarbonate diol, or polycaprolactone diol
- the elastic modulus of the cured film decreases and flexibility Tends to improve.
- the binder resin may have a carboxy group in the molecule. By having a carboxy group, the binder resin reacts with the component (b) described below, so that the heat resistance and chemical resistance of the cured film tend to be improved.
- the solubility in an alkali developing solution is improved, so that it is possible to form a fine pattern in a short development time.
- the acid value of the binder resin is preferably 5 to 200 mgKOH / g, more preferably 15 to 100 mgKOH / g. Since the crosslinked structure with the component (b) is densely formed by the binder resin having an appropriate acid value, the heat resistance, insulation reliability and chemical resistance of the cured film can be improved.
- a polymer having a carboxy group in the molecule can be obtained, for example, by using a compound having two hydroxyl groups and one carboxy group in the molecule as a diol component for forming a urethane polymer.
- the diol compound having two hydroxyl groups and one carboxy group include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid and 2,2-bis (3- Hydroxypropyl) propionic acid, 2,3-dihydroxy-2-methylpropionic acid, 2,2-bis (hydroxymethyl) butanoic acid, 2,2-bis (2-hydroxyethyl) butanoic acid, 2,2-bis Aliphatic diols such as (3-hydroxypropyl) butanoic acid, 2,3-dihydroxybutanoic acid, 2,4-dihydroxy-3,3-dimethylbutanoic acid, and 2,3-dihydroxyhexadecanoic acid; 2,3- Dihydroxybenzoic acid, 2,4-dihydroxy
- the binder resin may have an ethylenically unsaturated group in the molecule.
- the ethylenically unsaturated group include a vinyl group and a (meth) acryloyl group.
- (meth) acryl means acryl or methacryl
- (meth) acryloyl means acryloyl or methacryloyl.
- the binder resin has a photocurable functional group such as a (meth) acryloyl group
- a photocurable film can be formed from the resin composition.
- the resin composition contains the component (d) described below
- the binder resin having a photocurable functional group also reacts with the component (d), so that the crosslink density of the photocured film is increased and the heat resistance and Chemical resistance tends to improve.
- the photocrosslinking density By increasing the photocrosslinking density, the elution of the flame retardant into the developer or the like tends to be suppressed.
- the polymer having a (meth) acryloyl group in the molecule is, for example, a compound containing a hydroxyl group and at least one (meth) acryloyl group in the molecule in addition to a diol component and a diisocyanate component for forming a urethane polymer, And / or is obtained by using a compound containing an isocyanate group and at least one (meth) acryloyl group in the molecule.
- Examples of the compound having a hydroxyl group and a (meth) acryloyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 2-hydroxy-3-phenoxy.
- Examples of the compound having an isocyanate group and a (meth) acryloyl group in the molecule include 2- (meth) acryloyloxyethyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate and 2- (2-methacryloyloxyethyloxy). Examples thereof include ethyl isocyanate.
- the binder resin may have two or more photocurable functional groups in one molecule.
- a compound having one hydroxyl group and one (meth) acryloyl group in one molecule is used, and if the ratio is increased, both ends of the polymer chain ( A urethane di (meth) acrylate having a (meth) acryloyl group is obtained.
- the content of the component (a) in the resin composition is 10 parts by weight based on 100 parts by weight of the total solid content.
- the amount is preferably -80 parts by weight, more preferably 20-70 parts by weight, still more preferably 30-60 parts by weight.
- thermosetting resin is a compound having at least one thermosetting functional group in the molecule.
- thermosetting resin include epoxy resin, oxetane resin, isocyanate resin, blocked isocyanate resin, bismaleimide resin, bisallylnadiimide resin, polyester resin (for example, unsaturated polyester resin), diallyl phthalate resin, silicon resin, vinyl ester.
- Resin melamine resin, polybismaleimide triazine resin (BT resin), cyanate resin (for example, cyanate ester resin), urea resin, guanamine resin, sulfamide resin, aniline resin, polyurea resin, thiourethane resin, polyazomethine resin, episulfide resin , Ene-thiol resin, benzoxazine resin and the like.
- a polyfunctional epoxy resin having two or more epoxy groups in one molecule is preferable because it can impart heat resistance to the cured film and can impart adhesiveness to a conductor such as a metal foil or a circuit board.
- the epoxy resin may be a modified epoxy resin with urethane, rubber, chelate, dimer acid or the like.
- a commercially available epoxy resin may be used as it is as the component (b).
- the epoxy equivalent of the epoxy resin (mass (g) of the compound containing 1 equivalent of epoxy group) is preferably 2000 or less, and more preferably 1500 or less.
- the weight average molecular weight of the epoxy resin is preferably about 150 to 2000, more preferably about 200 to 1500.
- the content of the component (b) in the resin composition is 1 to 70 parts by weight based on 100 parts by weight of the total solid content. Is preferred, 5 to 50 parts by weight is more preferred, and 10 to 20 parts by weight is even more preferred.
- the resin composition may contain a thermosetting resin curing agent and / or a curing accelerator.
- the curing agent include phenol novolac resin, cresol novolac resin, phenol resin such as naphthalene type phenol resin, amino resin, urea resin, melamine, and dicyandiamide.
- curing accelerator examples include phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine compounds, trimethanolamine, triethanolamine, and tetraethanolamine; 1,8-diaza-bicyclo [5,4,0] ] -7-Undecenium tetraphenylborate and other borate compounds; imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methyl Imidazoles such as imidazole, 2-heptadecyl imidazole, 2-isopropyl imidazole, 2,4-dimethyl imidazole, 2-phenyl-4-methyl imidazole; 2-methyl imidazoline, 2-ethyl imidazoline, 2-isopropyl imidazoline, 2- Fe Imidazolines such as loumidazoline, 2-undecylimid
- the resin composition contains an organic phosphorus compound (spiro ring diphosphonate compound) represented by the following general formula as a flame retardant.
- R 2 and R 5 are each independently a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or an anthryl group which may have a substituent.
- R 1 , R 3 , R 4 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent or a naphthyl group which may have a substituent. , Or an anthryl group which may have a substituent.
- the above organophosphorus compound can be produced, for example, by the method described in JP-A-2004-35480.
- an insulating film exhibiting excellent flame retardancy can be obtained by adding a small amount of the flame retardant. Since the amount of the flame retardant added is small, it is possible to suppress a decrease in heat resistance and film strength due to the addition of the flame retardant.
- the thermal decomposition behavior of the polymer and the flame retardant are matched. For example, since free radicals generated by thermal decomposition of the polymer are trapped by the flame retardant, it is considered that one of the factors contributing to the improvement of flame retardancy is that the chain reaction can be stopped in the initial stage of combustion.
- the flame retardance and the adhesiveness of the photocured film are less likely to change before and after alkali development, and the flame retardant is used. Bleed out is also unlikely to occur.
- the flame retardant is an organic phosphorus compound, so it has high compatibility with the binder resin, and the flame retardant is a solid at room temperature and is eluted into the alkali developer. There are some difficult things.
- a cured film containing a flame retardant tends to have lower flexibility and inferior flex resistance as the content of the flame retardant increases.
- the urethane polymer as the component (a) and the component (c)
- the resin composition of the present invention can be suitably used for forming an insulating protective film of a flexible printed wiring board for a foldable device.
- the content of the component (c) in the resin composition is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, still more preferably 10 to 30 parts by weight, based on 100 parts by weight of the total solid content.
- the above-mentioned spiro-ring diphosphonate-based compound is more likely to exhibit a flame retardant effect than the inorganic phosphorus-based compound even in a small amount. Therefore, the content of the component (c) in the resin composition may be 20 parts by weight or less or 15 parts by weight or less.
- the amount of phosphorus atoms contained in the total solid content of the resin composition is preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight, and even more preferably 1.5 to 5% by weight.
- the content of phosphorus atoms may be 4% by weight or less or 3% by weight or less.
- the resin composition may contain a photocurable compound.
- the resin composition has photosensitivity.
- the photocurable compound also reacts with the component (a), so that the crosslink density of the photocured film is increased, and heat resistance and chemical resistance tend to be improved. is there.
- the photocurable compound has at least one photocurable functional group.
- the photocurable functional group is preferably an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include (meth) acryloyl group and vinyl group.
- the component (d) preferably has two or more photocurable functional groups in one molecule.
- a component having a lower molecular weight than the component (a) is used as the component (d).
- the weight average molecular weight of the component (d) is preferably 2000 or less, more preferably 1500 or less, and further preferably less than 1000.
- the functional group equivalent (mass (g) of the compound containing 1 equivalent of an ethylenically unsaturated group) of the component (d) is preferably 1000 or less, more preferably 750 or less, and further preferably 500 or less.
- polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in one molecule ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-1- (meth) Acryloxy-3- (meth) acryloxypropane, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acr Rate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth
- the resin composition contains the component (d)
- its content is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and more preferably 10 to 10 parts by weight based on 100 parts by weight of the total solid content of the resin composition. 30 parts by weight is more preferable.
- the resin composition preferably contains (e) a photopolymerization initiator.
- the photopolymerization initiator is a compound that absorbs and activates light energy such as UV (ultraviolet light) to start and accelerate the reaction of the radically polymerizable group.
- the resin composition contains a photopolymerization initiator, the resin composition can be used as a photosensitive resin composition.
- photoradical polymerization initiator examples include self-cleaving photoradical polymerization initiators such as benzoin compounds, acetophenones, aminoketones, oxime esters, acylphosphine oxide compounds, and azo compounds; and benzophenones and benzoins. Hydrogen abstraction type photoradicals of ethers, benzyl ketals, dibenzosuberones, anthraquinones, xanthones, thioxanthones, halogenoacetophenones, dialkoxyacetophenones, hydroxyacetophenones, halogenobisimidazoles, halogenotriazines, etc.
- a polymerization initiator may be used.
- the content of the component (e) in the resin composition may be set appropriately. From the viewpoint of enhancing the photosensitivity and preventing overexposure, the content of the component (e) is preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the components (a) and (d), 0.3 to 5 parts by weight is more preferable, and 0.5 to 3 parts by weight is still more preferable.
- the insulating film formed of the resin composition can be colored arbitrarily.
- the colorant is either a dye or a pigment.
- colorants include blue colorants, red colorants, yellow colorants, orange colorants, and purple colorants.
- Insulating films of various colors can be formed by combining a plurality of colorants. For example, a black colorant and a black colorant can be obtained by combining a blue pigment, an orange pigment, and a purple pigment.
- the blue colorant for example, C.I. which is a phthalocyanine-based, anthraquinone-based, or dioxazine-based pigment.
- C.I. which is a phthalocyanine-based, anthraquinone-based, or dioxazine-based pigment.
- Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97 which is a dye system.
- metal-substituted or unsubstituted phthalocyanine compounds can also be used as the blue colorant.
- orange colorants examples include C.I. I. Pigment Orange 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73.
- purple colorants examples include C.I. I. Pigment Violet 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; Solvent Violet 13, 36.
- the content of the component (f) may be appropriately set according to the type of colorant and the color of the insulating film. For example, about 1 to 10 parts by weight with respect to 100 parts by weight of the total solid content of the resin composition. And may be about 2 to 7 parts by weight, or about 3 to 5 parts by weight.
- the resin composition may contain a solvent in addition to the components (a) to (f).
- the solvent is not particularly limited as long as it can dissolve a resin component such as a binder polymer, and sulfoxides, formamides, acetamides, pyrrolidones, acetates, ethers, hexamethylphosphoramide, ⁇ -butyrolactone, etc.
- the polar organic solvent of is preferably used. These polar organic solvents may be used in combination with aromatic hydrocarbons such as xylene and toluene.
- the resin composition may contain various additives such as a defoaming agent, a leveling agent, an adhesion imparting agent, a stabilizer, and a filler, if necessary.
- a defoaming agent such as acrylic compounds, vinyl compounds, silicone compounds and the like.
- a resin composition is prepared by mixing the above components.
- Each of the above components may be subjected to operations such as pulverization / dispersion and defoaming before and / or after mixing, if necessary.
- the pulverization / dispersion may be carried out, for example, by using a kneading device such as a bead mill, a ball mill, or a triple roll.
- An insulating film can be formed by applying a resin composition (solution) on a substrate and drying a solvent as needed.
- a printed wiring board is used as the substrate.
- the printed wiring board may be a flexible printed wiring board using a flexible substrate such as a polyimide film.
- the resin composition may be applied onto the substrate by screen printing, curtain roll, reverse roll, spray coating, spin coating using a spinner, or the like.
- the thickness of the coating film may be adjusted so that the thickness after drying is about 5 to 100 ⁇ m, preferably 10 to 100 ⁇ m.
- the drying temperature is preferably 120 ° C. or lower, more preferably 40 to 100 ° C., from the viewpoint of suppressing the thermosetting reaction.
- the dried coating film may be used as it is as an insulating film. From the viewpoint of improving the heat resistance and chemical resistance of the insulating film, it is preferable to cure by heat curing and / or light curing.
- the component (b) When forming a thermosetting film, the component (b) may be cured by heat treatment of the coating film.
- the component (a) has a carboxy group
- the crosslinking density is increased by reacting the component (a) with the component (b).
- the curing temperature (maximum temperature at the time of thermal curing) is preferably 100 to 250 ° C. or less, more preferably 120 to 200 ° C., and 130 from the viewpoint of sufficiently promoting thermal curing and suppressing oxidation of metal wiring due to heat. It is more preferably up to 180 ° C.
- the coating film When forming a photo-cured film, the coating film may be exposed. At the time of exposure, a negative-type photomask is arranged on the coating film, and active rays such as ultraviolet rays, visible rays, and electron rays are irradiated to selectively cure the exposed portions. Next, by developing with a shower, paddle, dipping or the like, the non-exposed portion is dissolved, so that a pattern cured film is formed.
- active rays such as ultraviolet rays, visible rays, and electron rays
- an alkaline aqueous solution is used as the developing solution.
- the component (a) has a carboxy group and a photocurable functional group
- the component (a) has alkali solubility in the unexposed coating film and the component (a) is photocured in the coating film after exposure. Therefore, it has no alkali solubility. Therefore, when a photomask is arranged to perform exposure and development is performed using an alkali developing solution, the unexposed portion is dissolved in the developing solution, so that a patterned cured film is formed.
- the spiro-ring diphosphonate-based flame retardant as the component (c) is difficult to elute in an alkaline developer, the characteristics such as flame retardancy and adhesion of the cured film can be maintained even after alkaline development. .
- alkaline compound of the developer examples include alkali metals, alkaline earth metals, ammonium ions, hydroxides, carbonates, hydrogen carbonates, amine compounds and the like.
- alkali compound examples include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxy.
- the developing solution may contain an organic solvent miscible with water, such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone.
- the alkali concentration of the developer is generally 0.01 to 20% by weight, preferably 0.02 to 10% by weight, and the temperature of the developer is generally 0 to 80 ° C, preferably 10 to 60 ° C.
- the patterned cured film (relief pattern) after development is preferably rinsed with a rinse liquid such as water or an acidic aqueous solution.
- the insulating film may be heat-cured by heating after photo-curing.
- the coating film after photocuring has thermosetting property because the thermosetting functional group such as the epoxy group of the component (b) remains unreacted.
- the carboxy group of the component (a) reacts with the epoxy group of the component (b) and the like, so that a crosslinked network of the binder resin and the thermosetting resin is formed, and the heat resistance of the cured film is improved.
- the curing temperature is preferably 100 to 250 ° C., more preferably 120 to 200 ° C., and 130 to 180 ° C. from the viewpoint of sufficiently promoting the thermal curing and suppressing the oxidation of the metal wiring due to heat. More preferable.
- the cured film obtained from the resin composition has excellent heat resistance and flame retardancy, and is therefore suitably used as a surface protective material for printed circuit boards. Further, since the cured film is excellent in flexibility, it is also suitably used as a cured film of a flexible printed board having metal wiring on a flexible film such as a polyimide film.
- Synthesis example In the following synthesis examples, a polymer having a carboxy group in the molecule was polymerized. The properties of the polymers obtained in Synthesis Examples 1 and 2 were evaluated by the following methods.
- polycarbonate diol manufactured by Asahi Kasei Corporation, trade name: PCDL T5652, weight average molecular weight 2000
- PCDL T5652 weight average molecular weight 2000
- 2,2-bis (hydroxymethyl) butanoic acid 3.70 g ( 0.025 mol)
- a solution of 13.02 g (0.100 mol) of 2-hydroxyethyl methacrylate in 40.00 g of methyl triglyme were added over 1 hour.
- This solution was heated and stirred at 80 ° C. for 5 hours to obtain a solution of a urethane polymer (a1) containing a carboxy group in the molecule and having a methacryloyl group at the terminal.
- the solid content concentration of the solution was 52%
- the weight average molecular weight of the polymer was 8,600
- the acid value was 18 mgKOH / g.
- Parts of a photopolymerization initiator (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3) was added to each resin composition.
- a flame retardancy test was conducted as follows in accordance with the flame retardancy UL94 standard. Cut a polyimide film with a cured film into a width of 50 mm and a length of 200 mm, put a marked line in the center part of the length direction (at a position of 125 mm), and round it into a cylinder so that the cured film side is on the outside, rather than the marked line. A tape was adhered to the upper overlapping portion (a portion of 75 mm in the length direction) and the upper portion so that there was no gap, to prepare a cylinder for flame retardancy test.
- Adhesion of the cured film was evaluated according to the cross-cut tape method of JIS K5400 using a polyimide film having a cured film (before and after development) as a sample.
- the tape peeling test was repeated 5 times for one sample, and the following area was evaluated based on the remaining area ratio (residual film ratio) of the cured film in the sample after the test.
- C The residual area ratio was 80% or more and less than 95
- the residual area ratio was less than 80%
- the polyimide film on which a cured film (after development) was formed was cut into a size of 5 mm ⁇ 100 mm, bent 180 ° so that the cured film was on the outside, and a load of 100 g was placed on the bent portion for 3 seconds. After removing the load, the bent portions were observed with an optical microscope to evaluate the presence or absence of cracks. This work was carried out until cracks were formed in the cured film, and the evaluation was made according to the following criteria. A: No cracks were generated even after 10 bendings B: Cracks were generated at 2 to 9 bendings C: Cracks were generated at 1 bending
- the resin composition was applied onto a polyimide film and dried at 80 ° C. for 20 minutes to prepare a polyimide film having a coating film (B stage film) formed thereon.
- the two films were superposed so that the coating films were in contact with each other, and the state when peeled off was observed and evaluated according to the following criteria.
- the pattern was etched, immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute to surface-treat the copper foil, and then washed with pure water to prepare a flexible printed wiring board.
- a resin composition is applied to the wiring formation surface of this flexible printed wiring board by screen printing so that the final dry thickness is 20 ⁇ m, and dried, exposed, developed, washed, and heated in the same manner as above to form a cured film.
- the terminal of the wiring of this sample was connected to a power source, a direct current of 100 V was applied for 1000 hours in an environmental tester at 85 ° C. and 85% RH, and then the sample was visually observed and evaluated according to the following criteria.
- A No abnormalities such as swelling or bleeding were observed on the surface of the test piece and copper wiring.
- B Abnormalities such as swelling or oozing were observed on the surface of the test piece and / or copper wiring.
- Table 1 shows the compositions of the resin compositions of Examples and Comparative Examples (formulation and P atom content relative to the total solid content) and the evaluation results in a list. The shaded items in Table 1 have not been evaluated. Details of each component are as shown below.
- Example 1 and Example 2 using the spiro-ring diphosphonate flame retardant were excellent in flame retardancy. Further, from the comparison between Example 1 and Comparative Examples 1 to 6, it can be seen that the flame retardancy is improved by adding a small amount of the spiro ring diphosphonate flame retardant. It is considered that this is because the radical trap mechanism of the flame retardant effectively acted on the free radicals generated at the start of combustion.
- Example 1 the cured film exhibited high adhesiveness, and the adhesiveness and heat resistance did not decrease even after alkali development. Moreover, in Examples 1 and 2, the same good bending resistance as that of Reference Example 1 containing no flame retardant was exhibited, and the decrease of the bending resistance due to the addition of the flame retardant did not occur.
- Comparative Examples 7 and 8 in which the acrylic polymer was used as the binder resin and the spiro-ring diphosphonate flame retardant was added, the flame retardancy, adhesiveness, and tackiness were good as in Examples 1 and 2. However, in Comparative Examples 7 and 8, the crease resistance decreased as the amount of the flame retardant added increased.
- the spiro-ring diphosphonate flame retardant was added to the resin composition containing the urethane binder, specifically, it has excellent flame retardancy and adhesion, and also has excellent flexibility. It can be seen that a film can be formed.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Abstract
Description
バインダー樹脂は、有機溶媒に対して可溶性であり、ポリエチレングリコール換算の重量平均分子量が1,000以上、1,000,000以下のポリマーである。バインダー樹脂の重量平均分子量は、2,000~200,000がより好ましく、3,000~100,000がさらに好ましく、4,000~50,000が特に好ましい。バインダー樹脂の重量平均分子量が上記範囲内であれば、耐熱性と柔軟性に優れる硬化膜が得られやすい。
熱硬化性樹脂は、分子内に少なくとも1つの熱硬化性官能基を有する化合物である。熱硬化性樹脂としては、エポキシ樹脂、オキセタン樹脂、イソシアネート樹脂、ブロックイソシアネート樹脂、ビスマレイミド樹脂、ビスアリルナジイミド樹脂、ポリエステル樹脂(例えば不飽和ポリエステル樹脂等)、ジアリルフタレート樹脂、珪素樹脂、ビニルエステル樹脂、メラミン樹脂、ポリビスマレイミドトリアジン樹脂(BT樹脂)、シアネート樹脂(例えばシアネートエステル樹脂等)、ユリア樹脂、グアナミン樹脂、スルホアミド樹脂、アニリン樹脂、ポリウレア樹脂、チオウレタン樹脂、ポリアゾメチン樹脂、エピスルフィド樹脂、エン-チオール樹脂、ベンゾオキサジン樹脂等が挙げられる。硬化膜に耐熱性を付与できると共に、金属箔等の導体や回路基板に対する接着性を付与できることから、1分子中に2以上のエポキシ基を有する多官能エポキシ樹脂が好ましい。
樹脂組成物は、難燃剤として下記の一般式で表される有機リン系化合物(スピロ環ジホスホネート化合物)を含む。
樹脂組成物は、光硬化性化合物を含んでいてもよい。光硬化性化合物を含むことにより、樹脂組成物は感光性を有する。(a)バインダー樹脂が光硬化性官能基を有する場合、光硬化性化合物は(a)成分とも反応するため、光硬化膜の架橋密度が高められ、耐熱性や耐薬品性が向上する傾向がある。
(a)成分が光重合性官能基を有する場合、および/または樹脂組成物が(d)成分を含む場合、樹脂組成物は、(e)光重合開始剤を含有することが好ましい。光重合開始剤は、UV(紫外光)等の光エネルギーを吸収して活性化し、ラジカル重合性基の反応を開始・促進させる化合物である。樹脂組成物が光重合開始剤を含有することにより、樹脂組成物を感光性樹脂組成物として利用することができる。
樹脂組成物が(f)着色剤を含有することにより、樹脂組成物により形成される絶縁膜を任意に着色することができる。着色剤は、染料または顔料のいずれかである。着色剤としては、青色着色剤、赤色着色剤、黄色着色剤、橙色着色剤、紫色着色剤等が挙げられる。複数の着色剤を組み合わせることにより様々な色の絶縁膜を形成できる。例えば、青色顔料と橙色顔料と紫色顔料とを組み合わせることにより、黒色着色剤黒色着色剤とすることもできる。
樹脂組成物は、上記(a)~(f)成分の他に溶媒を含んでいてもよい。溶媒としては、バインダーポリマー等の樹脂成分を溶解できるものであれば特に限定されず、スルホキシド類、ホルムアミド類、アセトアミド類、ピロリドン類、アセテート類、エーテル類、ヘキサメチルホスホルアミド、γ-ブチロラクトン等の極性有機溶媒が好適に用いられる。これらの極性有機溶媒と、キシレン、トルエン等の芳香族炭化水素とを組み合わせて用いることもできる。
上記の各成分を混合することにより、樹脂組成物を調製する。上記の各成分は、混合前および/または混合後に、必要に応じて、粉砕・分散や、脱泡等の操作を行ってもよい。粉砕・分散は、例えば、ビーズミル、ボールミル、3本ロール等の混練装置を用いて実施すればよい。
樹脂組成物(溶液)を基板上に塗布し、必要に応じて溶媒を乾燥することにより絶縁膜を形成できる。基板としては、例えばプリント配線板が用いられる。プリント配線板の金属配線上に絶縁膜を形成することにより、絶縁信頼性が高められる。プリント配線板は、ポリイミドフィルム等の可撓性基板を用いたフレキシブルプリント配線板であってもよい。
以下の合成例では、分子内にカルボキシ基を有するポリマーを重合した。合成例1,2で得られたポリマーの特性は、以下の方法により評価した。
JIS K 5601-1-2に従って測定を行った。乾燥条件は170℃×1時間とした。
ゲルパーミエーションクロマトグラフィー(GPC)により、下記条件で測定を行った。
使用装置:東ソー HLC-8220GPC相当品
カラム:東ソー TSK gel Super AWM-H(6.0mm I.D.×15cm)×2本
ガードカラム:東ソー TSK guard column Super AW-H
溶離液:30mM LiBr + 20mM H3PO4 in DMF
流速:0.6mL/min
カラム温度:40℃
検出条件:RI:ポラリティ(+)、レスポンス(0.5sec)
試料濃度:約5mg/mL
分子量標準品:PEG(ポリエチレングリコール)
JIS K 5601-2-1に従って測定を行った。
攪拌機、温度計、滴下漏斗、および窒素導入管を備えた反応容器に、重合用溶媒として1,2-ビス(2-メトキシエトキシ)エタン(メチルトリグライム)40.00gおよびノルボルネンジイソシアネート20.62g(0.100モル)を仕込み、窒素気流下で攪拌しながら80℃に加温して溶解させた。この溶液に、ポリカーボネートジオール(旭化成株式会社製、商品名:PCDL T5652、重量平均分子量2000):50.00g(0.025モル)、2,2-ビス(ヒドロキシメチル)ブタン酸:3.70g(0.025モル)、および2-ヒドロキシエチルメタクリレート:13.02g(0.100モル)をメチルトリグライム:40.00gに溶解した溶液を1時間かけて添加した。この溶液を80℃で5時間加熱攪拌して、分子内にカルボキシ基を含有し、末端にメタクリロイル基を有するウレタンポリマー(a1)の溶液を得た。溶液の固形分濃度は52%、ポリマーの重量平均分子量は8,600、酸価は18mgKOH/gであった。
攪拌機、温度計、滴下漏斗、および窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム100.0gを仕込み、窒素気流下で攪拌しながら80℃に昇温した。これに、室温で予め混合しておいた、メタクリル酸12.0g(0.14モル)、メタクリル酸ベンジル28.0g(0.16モル)、メタクリル酸ブチル60.0g(0.42モル)、およびラジカル重合開始剤としてアゾビスイソブチロニトリル0.5gを、80℃に保温した状態で3時間かけて滴下漏斗から滴下した。滴下終了後、反応溶液を攪拌しながら90℃に昇温し、反応溶液の温度を90℃に保ちながらさらに2時間攪拌を行い、分子内にカルボキシ基を含有するアクリル系ポリマー(a2)の溶液を得た。溶液の固形分濃度は50%、ポリマーの重量平均分子量は48,000、酸価は78mgKOH/gであった。
表1に示す配合の組成物(単位は重量部)をメチルトリグライムに溶解させ、攪拌装置により撹拌した後、3本ロールミルで分散した。その後、脱泡装置で脱泡を行い、均一な溶液を調製した。溶媒としてのメチルトリグライムの量(上記合成例のポリマー溶液に含まれる溶媒も含めた全溶媒量)は、30重量部とした。各樹脂組成物には、表1に示す成分の他に、1.0重量部の光重合開始剤(エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(o-アセチルオキシム;BASF製「イルガキュア OXE02」)および0.1重量部のブタジエン系消泡剤(共栄社化学製「フローレン AC-2000」)を添加した。
<ポリイミドフィルム上への硬化膜の形成>
厚み25μmのポリイミドフィルム(カネカ製「アピカル25NPI」)上に、樹脂組成物を、スクリーン印刷により最終乾燥厚みが20μmになるように塗布し、80℃で20分乾燥した後、100mJ/cm2の積算露光量の紫外線を照射して露光した。次いで、30℃の1.0重量%炭酸ナトリウム水溶液を、1.0kgf/mm2の吐出圧で60秒スプレーして現像を行った。現像後、純水で十分洗浄した後、140℃のオーブン中で60分加熱して、ポリイミドフィルム上に硬化膜(現像後)を形成した。
硬化膜(現像前および現像後)を形成したポリイミドフィルムを試料として、難燃性UL94規格に従い、以下のように難燃性試験を行った。
硬化膜付きポリイミドフィルムを、幅50mm×長さ200mmに切り出し、長さ方向の中央部分(125mmの箇所)に標線を入れ、硬化膜側が外側となるように筒状に丸め、標線よりも上の重ね合わせ部分(長さ方向75mmの箇所)および上部に、隙間がないようにテープを貼り、難燃性試験用の筒を作製した。
A:5本全てがOKであったもの
B:5本中1~4本がOKであったもの
C:5本全てがNGであったもの
硬化膜(現像前および現像後)を形成したポリイミドフィルムを試料として、JIS K5400の碁盤目テープ法に準じて、硬化膜の密着性を評価した。1つの試料に対してテープ剥離試験を5回繰り返して行い、試験後の試料における硬化膜の残存面積率(残膜率)から、下記の基準で評価を行った。
A:剥がれがみられなかったもの(残存面積率100%)
B:剥離がみられたが、残存面積率が95%以上であったもの
C:残存面積率が80%以上95未満であったもの
D:残存面積率が80%未満であったもの
A:折り曲げ10回でもクラックが発生しなかったもの
B:折り曲げ2回以上9回以下でクラックが発生したもの
C:折り曲げ1回でクラックが発生したもの
上記と同様にして、ポリイミドフィルム上に樹脂組成物を塗布し、80℃で20分乾燥し、塗膜(Bステージ膜)が形成されたポリイミドフィルムを作製した。塗膜同士が接するように2枚のフィルムを重ね合わせ、引き剥がしたときの状態を観察し、下記の基準により評価した。
A:塗膜同士の貼り付きがなく、塗膜に貼り付き跡も残っていなかったもの
B:塗膜同士が貼り付き剥がした後に跡が残っていたもの、または塗膜同士が完全に貼り付いて引き剥がせなかったもの
厚み25μmのポリイミドフィルム(カネカ製「アピカル25NPI」)と厚み12μmの電解銅箔とをポリイミド系接着剤により張り合わせたフレキシブル銅張積層板の銅箔を、ライン幅/スペース幅=100μm/100μmの櫛形パターンにエッチングし、10容量%の硫酸水溶液中に1分間浸漬して銅箔の表面処理を行った後、純水で洗浄してフレキシブルプリント配線板を作製した。このフレキシブルプリント配線板の配線形成面に、脂組成物を、スクリーン印刷により最終乾燥厚みが20μmになるように塗布し、上記と同様に、乾燥、露光、現像、洗浄および加熱を行い、硬化膜付きフレキシブルプリント配線板を得た。この試料の配線の端子を電源に接続し、85℃、85%RHの環境試験機中で100Vの直流電流を1000時間印加した後、試料を目視にて観察し、下記の基準により評価した。
A:試験片表面および銅配線上に、膨れ、染み出し等の異常がみられなかったもの
B:試験片表面および/または銅配線上に、膨れ、染み出し等の異常が見られたもの
実施例および比較例の樹脂組成物の組成(配合、および固形分全量に対するP原子含有量)、ならびに評価結果を、表1に一覧で示す。なお、表1の斜線の項目は未評価である。各成分の詳細は以下に示す通りである。
<2>日立化成製「ファンクリル FA-321M」;EO変性ビスフェノールAジメタクリレート(平均分子量804)
<3>帝人製「ファイヤガード FCX-210」;スピロ環ジホスホネート系難燃剤
<4>クラリアント製「Exolit OP-935」;ホスフィン酸金属塩系難燃剤
<5>大塚化学製「SPB-100L」;ホスファゼン系難燃剤
<6>ナバルテック製「APYRAL AOH60」;水酸化アルミニウム系難燃剤
<7>大八木化学工業製「CR-733S」;リン酸エステル系難燃剤
<8>下記の青色顔料、橙色顔料および紫色顔料を、重量比1:1:1で混合した黒色顔料
青色顔料:BASF製 Pigment Blue 15:4
橙色顔料:クラリアント製 Pigment Orange 43
紫色顔料:クラリアント製 Pigment Violet 19
Claims (14)
- 前記(a)バインダー樹脂が、分子内にカルボキシ基を有する、請求項1に記載の樹脂組成物。
- 前記(a)バインダー樹脂の酸価が5~200mgKOH/gである、請求項2に記載の樹脂組成物。
- 前記(a)バインダー樹脂が、分子内にエチレン性不飽和基を有する、請求項1~3のいずれか1項に記載の樹脂組成物。
- さらに、(d)エチレン性不飽和基を有する化合物を含む、請求項1~4のいずれか1項に記載の樹脂組成物。
- さらに(e)光重合開始剤を含有する、請求項4または5に記載の樹脂組成物。
- さらに、(f)着色剤を含有する、請求項1~6のいずれか1項に記載の樹脂組成物。
- 前記(b)熱硬化性樹脂が多官能エポキシ樹脂である、請求項1~7のいずれか1項に記載の樹脂組成物。
- 全固形分100重量部に対する前記(c)難燃剤の含有量が、10~30重量部である、請求項1~8のいずれか1項に記載の樹脂組成物。
- 請求項1~9のいずれか1項に記載の樹脂組成物の硬化物からなる硬化膜。
- プリント配線板上に、請求項10に記載の硬化膜を備える硬化膜付きプリント配線板。
- 前記プリント配線板が可撓性を有する、請求項11に記載の硬化膜付きプリント配線板。
- 請求項1~9のいずれか1項に記載の樹脂組成物をプリント配線板の金属配線形成面に塗布して塗布膜を形成し、
前記塗布膜を加熱および/または露光することにより硬化する、硬化膜付きプリント配線板の製造方法。 - 請求項1~9のいずれか1項に記載の樹脂組成物をプリント配線板の金属配線形成面に塗布して塗布膜を形成し、
前記塗布膜の面内の少なくとも一部に活性光線を照射して光硬化を行い、
アルカリにより現像を行い、未硬化の前記塗布膜を溶解除去することにより、パターニングされた硬化膜を形成する、
硬化膜付きプリント配線板の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020553189A JP7418343B2 (ja) | 2018-10-19 | 2019-10-15 | 樹脂組成物、硬化膜、硬化膜付きプリント配線板およびその製造方法 |
CN201980068811.6A CN112888748B (zh) | 2018-10-19 | 2019-10-15 | 树脂组合物、固化膜、带固化膜的印刷电路板及其制造方法 |
KR1020217014578A KR20210080436A (ko) | 2018-10-19 | 2019-10-15 | 수지 조성물, 경화막, 경화막을 갖는 프린트 배선판 및 그의 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018197826 | 2018-10-19 | ||
JP2018-197826 | 2018-10-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020080352A1 true WO2020080352A1 (ja) | 2020-04-23 |
Family
ID=70282898
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/040438 WO2020080352A1 (ja) | 2018-10-19 | 2019-10-15 | 樹脂組成物、硬化膜、硬化膜付きプリント配線板およびその製造方法 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7418343B2 (ja) |
KR (1) | KR20210080436A (ja) |
CN (1) | CN112888748B (ja) |
TW (1) | TW202028354A (ja) |
WO (1) | WO2020080352A1 (ja) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002003727A (ja) * | 2000-06-22 | 2002-01-09 | Teijin Chem Ltd | 難燃性樹脂組成物 |
JP2003267984A (ja) * | 2002-03-12 | 2003-09-25 | Teijin Chem Ltd | ペンタエリスリトールジホスホネート化合物およびその製造方法 |
JP2008299293A (ja) * | 2007-06-04 | 2008-12-11 | Taiyo Ink Mfg Ltd | 感光性樹脂組成物及びそれを用いて得られるフレキシブル配線板 |
JP2017137405A (ja) * | 2016-02-03 | 2017-08-10 | 帝人株式会社 | 熱可塑性樹脂組成物およびその成形品 |
JP6263307B1 (ja) * | 2017-09-12 | 2018-01-17 | 株式会社レグルス | 熱膨張性樹脂組成物及び熱膨張性樹脂製材料 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001214024A (ja) * | 2000-02-04 | 2001-08-07 | Teijin Chem Ltd | 難燃性スチレン系樹脂組成物 |
US7205346B2 (en) * | 2001-11-30 | 2007-04-17 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
JP2004035481A (ja) * | 2002-07-04 | 2004-02-05 | Teijin Chem Ltd | スピロ環ジホスホネート化合物の製造方法 |
JP2004035480A (ja) * | 2002-07-04 | 2004-02-05 | Teijin Chem Ltd | スピロ環ジホスホネート化合物の製造方法 |
WO2007061080A1 (ja) * | 2005-11-25 | 2007-05-31 | Three Bond Co., Ltd. | 硬化性組成物 |
JP6006385B2 (ja) | 2015-08-05 | 2016-10-12 | 東芝テック株式会社 | サーバ |
WO2017188155A1 (ja) * | 2016-04-25 | 2017-11-02 | 株式会社カネカ | 熱硬化性樹脂組成物、硬化膜及びその製造方法、ならびに硬化膜付きフレキシブルプリント基板及びその製造方法 |
-
2019
- 2019-10-15 JP JP2020553189A patent/JP7418343B2/ja active Active
- 2019-10-15 CN CN201980068811.6A patent/CN112888748B/zh active Active
- 2019-10-15 WO PCT/JP2019/040438 patent/WO2020080352A1/ja active Application Filing
- 2019-10-15 KR KR1020217014578A patent/KR20210080436A/ko unknown
- 2019-10-17 TW TW108137463A patent/TW202028354A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002003727A (ja) * | 2000-06-22 | 2002-01-09 | Teijin Chem Ltd | 難燃性樹脂組成物 |
JP2003267984A (ja) * | 2002-03-12 | 2003-09-25 | Teijin Chem Ltd | ペンタエリスリトールジホスホネート化合物およびその製造方法 |
JP2008299293A (ja) * | 2007-06-04 | 2008-12-11 | Taiyo Ink Mfg Ltd | 感光性樹脂組成物及びそれを用いて得られるフレキシブル配線板 |
JP2017137405A (ja) * | 2016-02-03 | 2017-08-10 | 帝人株式会社 | 熱可塑性樹脂組成物およびその成形品 |
JP6263307B1 (ja) * | 2017-09-12 | 2018-01-17 | 株式会社レグルス | 熱膨張性樹脂組成物及び熱膨張性樹脂製材料 |
Also Published As
Publication number | Publication date |
---|---|
JP7418343B2 (ja) | 2024-01-19 |
CN112888748A (zh) | 2021-06-01 |
KR20210080436A (ko) | 2021-06-30 |
JPWO2020080352A1 (ja) | 2021-09-30 |
CN112888748B (zh) | 2023-09-22 |
TW202028354A (zh) | 2020-08-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI398458B (zh) | A photohardenable thermosetting resin composition, a dry film and a hardened product thereof, and a printed wiring board | |
JP5183540B2 (ja) | 硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板 | |
JP5997860B1 (ja) | 液状ソルダーレジスト組成物及びプリント配線板 | |
TWI458769B (zh) | A flame retardant photohardenable resin composition, a dry film and a cured product thereof, and a printed circuit board using the same | |
TWI519892B (zh) | 新穎感光性樹脂組合物及其利用 | |
TW201027242A (en) | Flame-retardant photocurable resin composition, dry film and cured product of the same, and printed wiring board using the composition, dry film or cured product | |
US20140147776A1 (en) | Photocurable/thermosetting resin composition | |
TW201219976A (en) | Kit for preparing new photosensitive resin composition and use thereof | |
WO2005071489A1 (ja) | 感光性樹脂組成物及びその硬化物 | |
JPWO2020203790A1 (ja) | フォトレジスト組成物およびその硬化物 | |
TWI435173B (zh) | A flame retardant photohardenable resin composition, a dry film and a hardened product, and a printed circuit board using the same | |
JP2013080050A (ja) | 感光性樹脂組成物、及びそれを用いた永久マスクレジストとその製造方法 | |
KR20130110070A (ko) | 난연성 경화성 수지 조성물, 드라이 필름, 난연성 피막 및 인쇄 배선판 | |
JP6892668B2 (ja) | 感光性樹脂組成物 | |
JP6829863B2 (ja) | 感光性樹脂組成物、及び被覆プリント配線板 | |
JP2006330235A (ja) | 難燃性ソルダーレジスト樹脂組成物及び絶縁保護被膜 | |
KR20150005427A (ko) | 경화성 수지 조성물, 그의 경화물, 그것을 갖는 프린트 배선판, 및 경화물의 제조 방법 | |
JP5847864B2 (ja) | 硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板 | |
JPWO2019160126A1 (ja) | 感光性樹脂組成物、硬化膜、プリント配線板およびその製造方法、ならびに感光性樹脂組成物作製キット | |
JP7418343B2 (ja) | 樹脂組成物、硬化膜、硬化膜付きプリント配線板およびその製造方法 | |
JP2013205624A (ja) | 感光性樹脂組成物、及びそれを用いた永久マスクレジストとその製造方法 | |
JP5506885B2 (ja) | 硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板 | |
JP6134188B2 (ja) | 黒色感光性樹脂組成物及びその利用 | |
JP5623586B2 (ja) | 硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板 | |
JP5575858B2 (ja) | 難燃性光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19873152 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2020553189 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20217014578 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19873152 Country of ref document: EP Kind code of ref document: A1 |