JP5526778B2 - Resin composition and film-forming material containing the same - Google Patents
Resin composition and film-forming material containing the same Download PDFInfo
- Publication number
- JP5526778B2 JP5526778B2 JP2009515186A JP2009515186A JP5526778B2 JP 5526778 B2 JP5526778 B2 JP 5526778B2 JP 2009515186 A JP2009515186 A JP 2009515186A JP 2009515186 A JP2009515186 A JP 2009515186A JP 5526778 B2 JP5526778 B2 JP 5526778B2
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- resin
- component
- resin composition
- group
- film
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 60
- 239000000463 material Substances 0.000 title claims description 22
- 229920005989 resin Polymers 0.000 claims description 82
- 239000011347 resin Substances 0.000 claims description 82
- 239000004962 Polyamide-imide Substances 0.000 claims description 36
- 229920002312 polyamide-imide Polymers 0.000 claims description 36
- 229920001721 polyimide Polymers 0.000 claims description 36
- 125000004018 acid anhydride group Chemical group 0.000 claims description 31
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 31
- 239000003822 epoxy resin Substances 0.000 claims description 31
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 31
- 229960001545 hydrotalcite Drugs 0.000 claims description 31
- 229920000647 polyepoxide Polymers 0.000 claims description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000009719 polyimide resin Substances 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 229920006122 polyamide resin Polymers 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- -1 isocyanate compound Chemical class 0.000 description 64
- 150000001875 compounds Chemical class 0.000 description 44
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 42
- 239000010408 film Substances 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- 239000010419 fine particle Substances 0.000 description 14
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 14
- 239000012948 isocyanate Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 13
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000007639 printing Methods 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 125000005442 diisocyanate group Chemical group 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 125000000962 organic group Chemical group 0.000 description 9
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- 229920002857 polybutadiene Polymers 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 229920006015 heat resistant resin Polymers 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012766 organic filler Substances 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 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 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
- 239000003054 catalyst Substances 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001296 polysiloxane Chemical group 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VLSVVMPLPMNWBH-UHFFFAOYSA-N Dihydro-5-propyl-2(3H)-furanone Chemical compound CCCC1CCC(=O)O1 VLSVVMPLPMNWBH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- AMNPXXIGUOKIPP-UHFFFAOYSA-N [4-(carbamothioylamino)phenyl]thiourea Chemical compound NC(=S)NC1=CC=C(NC(N)=S)C=C1 AMNPXXIGUOKIPP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical group C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- 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
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- 239000001294 propane Substances 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
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- 125000005591 trimellitate group Chemical group 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
-
- 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
- H05K3/285—Permanent coating compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- Non-Metallic Protective Coatings For Printed Circuits (AREA)
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Description
本発明は、樹脂組成物及びそれを含む被膜形成材料、特に、スクリーン印刷機、ディスペンサ、スピンコータ、などの塗布方法に適したチクソトロピー性を有する樹脂組成物及びそれを含む被膜形成材料に関する。 The present invention relates to a resin composition and a film-forming material containing the same, and more particularly to a resin composition having thixotropy suitable for a coating method such as a screen printer, a dispenser, a spin coater, and a film-forming material containing the same.
近年、電子部品の分野においては、小型化、薄型化、高速化への対応から、耐熱性、電気特性及び耐湿性に優れる被膜形成用材料用の樹脂として、エポキシ樹脂に代わり、ポリイミド樹脂、ポリアミドイミド樹脂、ポリアミド樹脂が使用されている。しかし、これらの樹脂は、樹脂構造が剛直であり、薄膜基材に用いた場合、硬化後の基材が大きく反り、硬化膜は柔軟性に欠け、屈曲性に劣る問題がある。 In recent years, in the field of electronic components, in response to miniaturization, thinning, and high speed, as a resin for film forming materials having excellent heat resistance, electrical characteristics, and moisture resistance, polyimide resin, polyamide instead of epoxy resin Imide resin and polyamide resin are used. However, these resins have a rigid resin structure, and when used as a thin film substrate, the cured substrate is greatly warped, and the cured film lacks flexibility and has poor flexibility.
そこで、上述の反り性、柔軟性を改善するために、樹脂を変性させて可撓化及び低弾性率化したポリアミドイミド樹脂(例えば、特許文献1、特許文献2及び特許文献3参照)が提案されている。これらの樹脂では、印刷性や作業性を向上させるために、無機フィラーや有機フィラー等を樹脂溶液に分散させている。また、基材と樹脂やフィラーと樹脂同士の密着性を向上させるために、各種カップリング剤や表面処理剤等の添加剤が使用されている。 Therefore, in order to improve the above-described warpage and flexibility, a polyamide-imide resin that has been modified to have a flexible and low elastic modulus by modifying the resin (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3) is proposed. Has been. In these resins, in order to improve printability and workability, inorganic fillers, organic fillers, and the like are dispersed in the resin solution. In addition, additives such as various coupling agents and surface treatment agents are used to improve the adhesion between the substrate and the resin or between the filler and the resin.
しかしながら、ポリイミドフィルムの片面に銅配線が施されてなるフレキシブル配線板の銅配線側の表面に、前述の被膜形成材料をスクリーン印刷し、その後硬化したものを巻き取る際、フレキシブル配線板の銅配線が施されていない側の表面に被膜形成材料からなる硬化被膜が貼り付くという問題があり、従来ではポリイミドフィルムと硬化被膜間にスペーサを設けているのが実情である。 However, when winding the above film-forming material on the surface of the copper wiring side of the flexible wiring board in which the copper wiring is applied on one side of the polyimide film and then winding the cured film, the copper wiring of the flexible wiring board There is a problem that a cured film made of a film-forming material adheres to the surface on which the film is not applied. Conventionally, a spacer is provided between the polyimide film and the cured film.
また、上記特許文献1〜3に開示の被膜形成材料を用いて硬化被膜を形成した配線板に高温高湿下で通電した場合、電極の黒膨れが発生し、電気特性を低下させる一因であると懸念されている。 In addition, when a circuit board having a cured film formed using the film-forming material disclosed in Patent Documents 1 to 3 is energized under high temperature and high humidity, black swelling of the electrode occurs, which is a cause of lowering electrical characteristics. There is concern about it.
本発明は、上記従来の事情に鑑みてなされたもので、その課題は、硬化後の被膜とポリイミドフィルムとの貼り付き性を低減でき、且つ高温高湿下の通電において電極の黒膨れを軽減できる樹脂組成物および該樹脂組成物を含む被膜形成材料を提供することにある。 The present invention has been made in view of the above-described conventional circumstances, and the problem is that the adhesion between the cured film and the polyimide film can be reduced, and the black swelling of the electrode can be reduced in energization under high temperature and high humidity. An object of the present invention is to provide a resin composition that can be formed and a film-forming material containing the resin composition.
前記課題を解決するために、本発明にかかる樹脂組成物は、(A)成分:酸無水物基及び/又はカルボキシル基を有する樹脂と、(B)成分:エポキシ樹脂と、(C)成分:ハイドロタルサイトを含むフィラーと、を含有することを特徴とする。 In order to solve the above-mentioned problems, the resin composition according to the present invention comprises (A) component: a resin having an acid anhydride group and / or carboxyl group, (B) component: epoxy resin, and (C) component: And a filler containing hydrotalcite.
前記構成の樹脂組成物において、前記(A)成分が、ポリカーボネート骨格を有することが好ましい。
さらに、前記(A)成分が、下記一般式(1)In the resin composition having the above configuration, the component (A) preferably has a polycarbonate skeleton.
Furthermore, the component (A) is represented by the following general formula (1)
さらに、(A)成分は、ポリカーボネート骨格を有するポリイミド樹脂、ポリアミドイミド樹脂、ポリアミド樹脂から選択される少なくとも1種の樹脂のイソシアネート残基と、酸無水物基を有する3価以上のポリカルボン酸またはその誘導体とを反応させて得られた樹脂であることが好ましい。 Further, the component (A) is a trivalent or higher polycarboxylic acid having an isocyanate residue and an acid anhydride group of at least one resin selected from a polyimide resin having a polycarbonate skeleton, a polyamideimide resin, and a polyamide resin. A resin obtained by reacting the derivative is preferable.
また、前記構成の樹脂組成物において、(C)成分の含有量が、(A)成分100重量部に対して、10〜50質量%であり、前記(C)成分中に占めるハイドロタルサイトの含有率が10〜50質量%であることが好ましい。 Moreover, in the resin composition of the said structure, content of (C) component is 10-50 mass% with respect to 100 weight part of (A) component, and the hydrotalcite which occupies in said (C) component The content is preferably 10 to 50% by mass.
また、本発明の樹脂組成物は、銅箔をポリイミド基材に積層したフレキシブルプリント基板の保護膜用として好適に用いられる。 Moreover, the resin composition of this invention is used suitably for the protective film use of the flexible printed circuit board which laminated | stacked copper foil on the polyimide base material.
本発明の被膜形成材料は、前記本発明の樹脂組成物を含むことを特徴とする。 The film forming material of the present invention includes the resin composition of the present invention.
本発明の樹脂組成物は、硬化後の被膜とポリイミドフィルムとの貼り付き性を低減でき、且つ高温高湿下の通電において電極の黒膨れを軽減できるため、フレキシブル配線板などの電子部品に好適に用いることができ、信頼性の高い電子部品が得られるという効果を奏する。 The resin composition of the present invention is suitable for electronic components such as flexible wiring boards because it can reduce the adhesion between the cured film and the polyimide film, and can reduce the black swelling of the electrode when energized under high temperature and high humidity. The electronic component can be used in a highly reliable electronic component.
本発明の樹脂組成物は、前述のように、(A)成分:酸無水物基を及び/又はカルボキシル基を有する樹脂と、(B)成分:エポキシ樹脂と、(C)成分:ハイドロタルサイトを含むフィラーとを必須成分として含有する。以下、各必須成分について詳しく説明する。 As described above, the resin composition of the present invention comprises (A) component: resin having an acid anhydride group and / or carboxyl group, (B) component: epoxy resin, and (C) component: hydrotalcite. And a filler containing the above as an essential component. Hereinafter, each essential component will be described in detail.
〔(A)成分:酸無水物基及び/又はカルボキシル基を有する樹脂〕
(A)成分である「酸無水物基及び/又はカルボキシル基を有する樹脂」としては、ブタジエン構造やシリコーン構造を有するエポキシ樹脂、フェノール樹脂、アクリル樹脂、ポリウレタン、ポリブタジエン、水添加ポリブタジエン、ポリエステル、ポリカーボネート、ポリエーテル、ポリスルホン、ポリテトラフルオロ樹脂、ポリシリコーン、メラミン樹脂、ポリアミド、ポリアミドイミド、ポリイミド等の樹脂の主鎖及び/又は側鎖に酸無水物基及び/又はカルボキシル基を導入したものが挙げられる。これらは、単独又は2種類以上組み合わせて使用することができる。また、酸無水物基及び/又はカルボキシル基を有する樹脂と酸無水物基及び/又はカルボキシル基を有さない樹脂を併用することもできる。[(A) component: resin having acid anhydride group and / or carboxyl group]
As the “resin having an acid anhydride group and / or carboxyl group” as the component (A), an epoxy resin having a butadiene structure or a silicone structure, a phenol resin, an acrylic resin, a polyurethane, a polybutadiene, a water-added polybutadiene, a polyester, or a polycarbonate , Polyether, polysulfone, polytetrafluororesin, polysilicone, melamine resin, polyamide, polyamideimide, polyimide and other resins having an acid anhydride group and / or carboxyl group introduced into the main chain and / or side chain. It is done. These can be used alone or in combination of two or more. In addition, a resin having an acid anhydride group and / or a carboxyl group and a resin having no acid anhydride group and / or a carboxyl group can be used in combination.
上記カルボキシル基を導入する方法としては、ブタジエン構造やシリコーン構造を有するエポキシ樹脂、フェノール樹脂、アクリル樹脂、ポリウレタン、ポリブタジエン、水添加ポリブタジエン、ポリエステル、ポリカーボネート、ポリエーテル、ポリスルホン、ポリテトラフルオロ樹脂、ポリシリコーン、メラミン樹脂、ポリアミド、ポリアミドイミド、ポリイミド樹脂等の合成過程において、ラジカル重合、縮重合又はイオン重合可能なカルボキシル基を有する化合物を用いることで得ることができる。 As a method for introducing the carboxyl group, epoxy resins having a butadiene structure or a silicone structure, phenol resins, acrylic resins, polyurethanes, polybutadienes, water-added polybutadienes, polyesters, polycarbonates, polyethers, polysulfones, polytetrafluororesins, polysilicones In the synthesis process of melamine resin, polyamide, polyamideimide, polyimide resin, etc., it can be obtained by using a compound having a carboxyl group capable of radical polymerization, condensation polymerization or ion polymerization.
また、上記酸無水物基を導入する方法としては、ブタジエン構造やシリコーン構造を有するエポキシ樹脂、フェノール樹脂、アクリル樹脂、ポリウレタン、ポリブタジエン、水添加ポリブタジエン、ポリエステル、ポリカーボネート、ポリエーテル、ポリスルホン、ポリテトラフルオロ樹脂、ポリシリコーン、メラミン樹脂、ポリアミド、ポリアミドイミド、ポリイミド樹脂等由来のエポキシ残基、イソシアネート残基、水酸基残基及びカルボキシル基等と下記一般式(2)及び/又は一般式(3)
で表される化合物とを反応させて得ることができる。In addition, the acid anhydride group can be introduced by using an epoxy resin having a butadiene structure or a silicone structure, a phenol resin, an acrylic resin, a polyurethane, a polybutadiene, a water-added polybutadiene, a polyester, a polycarbonate, a polyether, a polysulfone, or a polytetrafluoro. Epoxy residues, isocyanate residues, hydroxyl groups and carboxyl groups derived from resins, polysilicones, melamine resins, polyamides, polyamideimides, polyimide resins, etc. and the following general formula (2) and / or general formula (3)
It can obtain by making it react with the compound represented by these.
樹脂の末端及び又は側鎖に酸無水物基及び/又はカルボキシル基を導入することにより、後述する(B)成分であるエポキシ樹脂と反応性が高くなるため、スペーサーとソルダレジストとの貼り付き性を向上することができる。 By introducing an acid anhydride group and / or carboxyl group into the terminal and / or side chain of the resin, the reactivity with the epoxy resin, which is the component (B) described later, is increased, so that the sticking property between the spacer and the solder resist is increased. Can be improved.
また、本発明の(A)成分の樹脂は、主にフレキシブル基板にも対応させるため、可撓性及び低弾性率であることが好ましい。(A)成分の樹脂を可撓性及び低弾性率にするためには、樹脂の主鎖に可撓性を向上できる成分を導入することが挙げられ、そのような成分としては、例えば、ポリブタジエン骨格、シリコーン樹脂骨格及び/又はポリカーボネート骨格が好ましい。 In addition, the resin of the component (A) of the present invention is preferably flexible and has a low elastic modulus so as to mainly correspond to a flexible substrate. In order to make the resin of component (A) flexible and have a low elastic modulus, introduction of a component capable of improving flexibility into the main chain of the resin can be mentioned, and as such a component, for example, polybutadiene A skeleton, a silicone resin skeleton, and / or a polycarbonate skeleton are preferable.
また、硬化被膜の耐熱性、電気特性、耐湿性、耐溶剤性及び耐薬品性を向上させるためには、樹脂の主鎖中に耐熱性を向上できる成分を導入することが挙げられ、そのような成分としては、例えば、ポリイミド、ポリアミドイミド若しくはポリアミド又はこれらの骨格が好ましい。中でも、可撓化、低弾性率化及び高耐熱性化の観点から、ポリカーボネート骨格及びイミド骨格が好ましい。 In order to improve the heat resistance, electrical properties, moisture resistance, solvent resistance and chemical resistance of the cured coating, it is possible to introduce a component capable of improving heat resistance into the main chain of the resin. As such a component, for example, polyimide, polyamideimide or polyamide or a skeleton thereof is preferable. Among these, a polycarbonate skeleton and an imide skeleton are preferable from the viewpoint of flexibility, low elastic modulus, and high heat resistance.
本発明において、(A)成分として使用することができる「酸無水物基及び/又はカルボキシル基を有する樹脂」は、通常、1,6−ヘキサンジオール系ポリカーボネートジオール等と、カルボキシル基を有する化合物、酸無水物を有する化合物及び/又はイソシアネート基を有する化合物とを反応させることで得られる。 In the present invention, the “resin having an acid anhydride group and / or carboxyl group” that can be used as the component (A) is usually 1,6-hexanediol-based polycarbonate diol and the like, a compound having a carboxyl group, It can be obtained by reacting a compound having an acid anhydride and / or a compound having an isocyanate group.
また、本発明において、(A)成分として使用することができる「酸無水物基及び/又はカルボキシル基を有する樹脂」は、例えば、(a)成分:酸無水物基を有する3価のポリカルボン酸及びその誘導体、並びに酸無水物基を有する4価のポリカルボン酸から選ばれる1種以上の化合物と、(b)成分:イソシアネート化合物又はアミン化合物とを反応させて得られる。 In the present invention, “resin having an acid anhydride group and / or carboxyl group” that can be used as the component (A) is, for example, (a) component: trivalent polycarboxylic acid having an acid anhydride group. It can be obtained by reacting one or more compounds selected from acids and derivatives thereof and tetravalent polycarboxylic acids having an acid anhydride group and component (b): an isocyanate compound or an amine compound.
上記(a)成分である「酸無水物基を有する3価のポリカルボン酸及びその誘導体」は、特に限定されないが、例えば、下記式(4)及び(5): Although the “trivalent polycarboxylic acid having an acid anhydride group and its derivative” as the component (a) is not particularly limited, for example, the following formulas (4) and (5):
上記(a)成分の「酸無水物基を有する3価のポリカルボン酸」としては、耐熱性、コスト面等から、トリメリット酸無水物が、特に好ましい。 As the “trivalent polycarboxylic acid having an acid anhydride group” as the component (a), trimellitic acid anhydride is particularly preferable from the viewpoint of heat resistance, cost, and the like.
他方の「酸無水物基を有する4価のポリカルボン酸」としては、特に限定されないが、例えば、下記式(6): The other “tetravalent polycarboxylic acid having an acid anhydride group” is not particularly limited. For example, the following formula (6):
また、これらのほかに必要に応じて、酸成分として、脂肪族ジカルボン酸(コハク酸、グルタル酸、アジピン酸、アゼライン酸、スベリン酸、セバシン酸、デカン二酸、ドデカン二酸、ダイマー酸等)、芳香族ジカルボン酸(イソフタル酸、テレフタル酸、フタル酸、ナフタレンジカルボン酸、オキシジ安息香酸等)等を併用することができる。この場合、分子鎖中にアミド結合も形成される。 In addition to these, as necessary, an aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid, etc.) Aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.) can be used in combination. In this case, an amide bond is also formed in the molecular chain.
上記(b)成分として用いられるイソシアネート化合物は、例えば、下記式(8): The isocyanate compound used as the component (b) is, for example, the following formula (8):
上記式(8)で示される化合物(b−1)は、下記式(9): The compound (b-1) represented by the above formula (8) is represented by the following formula (9):
OCN−X−NCO (10)
(式中、Xは、二価の有機基である)で示されるジイソシアネート類とを反応させることにより得られる。
OCN-X-NCO (10)
It is obtained by reacting with a diisocyanate represented by the formula (wherein X is a divalent organic group).
上記式(10)中のXで示される二価の有機基としては、例えば、炭素数1〜20のアルキレン基、又は非置換若しくはメチル基等の炭素数1〜5の低級アルキル基で置換されているフェニレン基等のアリーレン基が挙げられる。上記アルキレン基の炭素数は、より好ましくは1〜18である。ジフェニルメタン−4,4’−ジイル基、ジフェニルスルホン−4,4’−ジイル基等の芳香族環を2つ有する基も好ましいものとして挙げられる。 Examples of the divalent organic group represented by X in the formula (10) include, for example, an alkylene group having 1 to 20 carbon atoms, or an unsubstituted or substituted lower alkyl group having 1 to 5 carbon atoms such as a methyl group. And an arylene group such as a phenylene group. The number of carbon atoms of the alkylene group is more preferably 1-18. Groups having two aromatic rings such as diphenylmethane-4,4'-diyl group and diphenylsulfone-4,4'-diyl group are also preferred.
上記の式(9)で示されるカーボネートジオール類としては、例えば、α,ω−ポリ(ヘキサメチレンカーボネート)ジオール、α,ω−ポリ(3−メチル−ペンタメチレンカーボネート)ジオール等が挙げられ、市販されているものとしては、ダイセル化学(株)製の商品名「PLACCEL CD−205,205PL,205HL,210,210PL,210HL,220,220PL,220HL」等が挙げられる。これらを単独で又は2種類以上を組み合わせて使用することができる。 Examples of the carbonate diols represented by the above formula (9) include α, ω-poly (hexamethylene carbonate) diol, α, ω-poly (3-methyl-pentamethylene carbonate) diol, and the like. Examples of such products include trade names “PLACCEL CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL” manufactured by Daicel Chemical Industries, Ltd. These can be used alone or in combination of two or more.
また、上記式(10)で示されるジイソシアネート類としては、例えば、ジフェニルメタン−2,4’−ジイソシアネート;3,2’−、3,3’−、4,2’−、4,3’−、5,2’−、5,3’−、6,2’−又は6,3’−ジメチルジフェニルメタン−2,4’−ジイソシアネート;3,2’−、3,3’−、4,2’−、4,3’−、5,2’−、5,3’−、6,2’−又は6,3’−ジエチルジフェニルメタン−2,4’−ジイソシアネート;3,2’−、3,3’−、4,2’−、4,3’−、5,2’−、5,3’−、6,2’−又は6,3’−ジメトキシジフェニルメタン−2,4’−ジイソシアネート;ジフェニルメタン−4,4’−ジイソシアネート;ジフェニルメタン−3,3’−ジイソシアネート;ジフェニルメタン−3,4’−ジイソシアネート;ジフェニルエーテル−4、4’−ジイソシアネート;ベンゾフェノン−4,4’−ジイソシアネート;ジフェニルスルホン−4,4’−ジイソシアネート;トリレン−2,4−ジイソシアネート;トリレン−2,6−ジイソシアネート;m−キシリレンジイソシアネート;p−キシリレンジイソシアネート;ナフタレン−2,6−ジイソシアネート;4,4’−〔2,2ビス(4−フェノキシフェニル)プロパン〕ジイソシアネート等が挙げられる。これらのジイソシアネート類において、式(8)中のXが芳香族環を有する芳香族ポリイソシアネートを使用することが好ましい。これらは、単独で又は2種類以上を組み合わせて使用することができる。 Examples of the diisocyanates represented by the above formula (10) include diphenylmethane-2,4′-diisocyanate; 3,2′-, 3,3′-, 4,2′-, 4,3′-, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate; 3,2'-, 3,3'-, 4,2'- 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate; 3,2'-, 3,3 ' -, 4,2'-, 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate; diphenylmethane-4 , 4'-diisocyanate; diphenylmethane-3,3'-diisocyanate; diphenyl Diphenyl ether-4,4'-diisocyanate; benzophenone-4,4'-diisocyanate; diphenylsulfone-4,4'-diisocyanate; tolylene-2,4-diisocyanate; tolylene-2,6 -Diisocyanate; m-xylylene diisocyanate; p-xylylene diisocyanate; naphthalene-2,6-diisocyanate; 4,4 '-[2,2bis (4-phenoxyphenyl) propane] diisocyanate. In these diisocyanates, it is preferable to use an aromatic polyisocyanate in which X in the formula (8) has an aromatic ring. These can be used alone or in combination of two or more.
また、式(10)で示されるジイソシアネート類としては、本発明の目的の範囲内で、ヘキサメチレンジイソシアネート、2,2,4−トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート、4,4’−ジシクロヘキシルメタンジイソシアネート、トランスシクロヘキサン−1,4−ジイソシアネート、水添m−キシリレンジイソシアネート、リジンジイソシアネート等の脂肪族又は脂環式イソシアネート、あるいは三官能以上のポリイソシアネートを使用することができる。 Further, as the diisocyanates represented by the formula (10), within the scope of the object of the present invention, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, Aliphatic or alicyclic isocyanates such as transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and lysine diisocyanate, or trifunctional or higher polyisocyanates can be used.
上記式(10)で示されるジイソシアネート類は、経日変化を避けるために必要なブロック剤で安定化したものを使用してもよい。ブロック剤としては、アルコール、フェノール、オキシム等があるが、特に制限はない。 Diisocyanates represented by the above formula (10) may be those stabilized with a blocking agent necessary to avoid changes over time. Examples of the blocking agent include alcohol, phenol and oxime, but there is no particular limitation.
上記式(9)で示されるカーボネートジオール類と上記式(10)で示されるジイソシアネート類との配合割合は、水酸基数とイソシアネート基数の比率が、イソシアネート基/水酸基=1.01以上になるようにすることが好ましい。 The mixing ratio of the carbonate diols represented by the above formula (9) and the diisocyanates represented by the above formula (10) is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is isocyanate group / hydroxyl group = 1.01 or more. It is preferable to do.
上記式(9)で示されるカーボネートジオール類と上記式(10)で示されるジイソシアネート類との反応は、無溶媒あるいは有機溶媒の存在下で行うことができる。反応温度は、60〜200℃とすることが好ましく、より好ましくは80〜180℃である。反応時間は、バッチの規模、採用される反応条件等により適宜選択することができる。例えば、1〜5L(リットル)のフラスコスケールで2〜5時間とすることができる。 The reaction of the carbonate diols represented by the above formula (9) and the diisocyanates represented by the above formula (10) can be carried out without solvent or in the presence of an organic solvent. The reaction temperature is preferably 60 to 200 ° C, more preferably 80 to 180 ° C. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like. For example, it can be 2 to 5 hours on a flask scale of 1 to 5 L (liter).
このようにして得られる化合物(b−1)(イソシアネート化合物)の数平均分子量は、500〜10,000であることが好ましく、1,000〜9,500であることがより好ましく、1,500〜9,000であることが特に好ましい。数平均分子量が500未満であると、反り性が悪化する傾向があり、10,000を超えると、イソシアネート化合物の反応性が低下し、ポリイミド樹脂化することが困難となる傾向がある。 The number average molecular weight of the compound (b-1) (isocyanate compound) thus obtained is preferably 500 to 10,000, more preferably 1,000 to 9,500, and 1,500. It is especially preferable that it is-9,000. When the number average molecular weight is less than 500, the warping property tends to be deteriorated. When the number average molecular weight exceeds 10,000, the reactivity of the isocyanate compound is lowered, and it tends to be difficult to obtain a polyimide resin.
なお、本明細書において、数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)によって測定し、標準ポリスチレンの検量線を用いて換算した値とする。また、本発明の数平均分子量及び分散度は、以下のように定義される。
a)数平均分子量(Mn)
Mn=Σ(NiMi)/Ni=ΣXiMi
(Xi=分子量Miの分子のモル分率=Ni/ΣNi)
b)重量平均分子量
Mw=Σ(NiMi 2)/ΣNiMi=ΣWiMi
(Wi=分子量Miの分子の重量分率=NiMi/ΣNiMi)
c)分子量分布(分散度)
分散度=Mw/Mn In the present specification, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. Moreover, the number average molecular weight and dispersion degree of this invention are defined as follows.
a) Number average molecular weight (M n )
M n = Σ (N i M i ) / N i = ΣX i M i
(X i = Mole fraction of molecules with molecular weight M i = N i / ΣN i )
b) Weight average molecular weight M w = Σ (N i M i 2 ) / ΣN i M i = ΣW i M i
(W i = weight fraction of molecules of molecular weight M i = N i M i / ΣN i M i )
c) Molecular weight distribution (dispersity)
Dispersity = M w / M n
上記(b)成分のイソシアネート化合物として、化合物(b−1)以外の化合物(以下、化合物(b−2)とする)を使用することもできる。化合物(b−2)としては、化合物(b−1)以外のイソシアネート化合物であれば、特に限定されず、例えば、上記式(9)で示されるジイソシアネート類、三価以上のポリイソシアネート類等が挙げられる。これらは、単独で又は2種類以上を組み合わせて使用することができる。化合物(b−2)のイソシアネート化合物の数平均分子量の好ましい範囲は、上記化合物(b−1)と同様である。 As the isocyanate compound of the component (b), a compound other than the compound (b-1) (hereinafter referred to as compound (b-2)) can also be used. The compound (b-2) is not particularly limited as long as it is an isocyanate compound other than the compound (b-1), and examples thereof include diisocyanates represented by the above formula (9), trivalent or higher polyisocyanates, and the like. Can be mentioned. These can be used alone or in combination of two or more. The preferred range of the number average molecular weight of the isocyanate compound of the compound (b-2) is the same as that of the compound (b-1).
特に耐熱性の点から、化合物(b−1)と化合物(b−2)とを併用することが好ましい。なお、化合物(b−1)及び化合物(b−2)をそれぞれ単独で用いる場合は、フレキシブル配線板用の保護膜としての柔軟性、反り性の改善等の点から、化合物(b−1)を使用することが好ましい。 In particular, from the viewpoint of heat resistance, it is preferable to use the compound (b-1) and the compound (b-2) in combination. In addition, when using a compound (b-1) and a compound (b-2) each independently, it is a compound (b-1) from points, such as a softness | flexibility as a protective film for flexible wiring boards, and a curvature improvement. Is preferably used.
化合物(b−2)としては、その総量の50〜100重量%が芳香族ポリイソシアネートであることが好ましく、耐熱性、溶解性、機械特性、コスト面等のバランスを考慮すれば、4,4’−ジフェニルメタンジイソシアネートが特に好ましい。 As compound (b-2), 50 to 100% by weight of the total amount is preferably aromatic polyisocyanate, and considering the balance of heat resistance, solubility, mechanical properties, cost, etc., 4, 4 '-Diphenylmethane diisocyanate is particularly preferred.
化合物(b−1)と化合物(b−2)を併用する場合、化合物(b−1)/化合物(b−2)の当量比で0.1/0.9〜0.9/0.1とすることが好ましく、0.2/0.8〜0.8/0.2とすることがより好ましく、0.3/0.7〜0.7/0.3とすることが特に好ましい。当量比がこの範囲にあると、良好な低反り性、密着性と良好な耐熱性等の膜特性をともに得ることができる。 When the compound (b-1) and the compound (b-2) are used in combination, the equivalent ratio of compound (b-1) / compound (b-2) is 0.1 / 0.9 to 0.9 / 0.1. Is preferable, 0.2 / 0.8 to 0.8 / 0.2 is more preferable, and 0.3 / 0.7 to 0.7 / 0.3 is particularly preferable. When the equivalence ratio is within this range, film properties such as good low warpage, adhesion and good heat resistance can be obtained.
上記(b)成分のうちアミン化合物としては、上記(b)成分のイソシアネート化合物におけるイソシアナト基をアミノ基に転換した化合物が挙げられる。イソシアナト基のアミノ基への転換は、公知の方法により行うことができる。アミン化合物の数平均分子量の好ましい範囲は、上記化合物(b−1)と同様である。 Among the components (b), examples of the amine compound include compounds obtained by converting the isocyanate group in the isocyanate compound of the component (b) to an amino group. Conversion of the isocyanato group to an amino group can be performed by a known method. The preferred range of the number average molecular weight of the amine compound is the same as that of the compound (b-1).
また、(a)成分である「酸無水物基を有する三価のポリカルボン酸又はその誘導体及び/又は酸無水物基を有する4価のポリカルボン酸」の配合割合は、(b)成分中のイソシアネート基の総数に対する(a)成分中のカルボキシル基と酸無水物基の総数の比が、0.6〜1.4となるようにすることが好ましく、0.7〜1.3となるようにすることがより好ましく、0.8〜1.2となるようにすることが特に好ましい。この比が0.6未満又は1.4を超えると、ポリイミド結合を含む樹脂の分子量を高くすることが困難となる傾向がある。 In addition, the blending ratio of (a) component “trivalent polycarboxylic acid having acid anhydride group or derivative thereof and / or tetravalent polycarboxylic acid having acid anhydride group” is The ratio of the total number of carboxyl groups and acid anhydride groups in component (a) to the total number of isocyanate groups is preferably 0.6 to 1.4, and is preferably 0.7 to 1.3. More preferably, it is particularly preferably 0.8 to 1.2. When this ratio is less than 0.6 or exceeds 1.4, it tends to be difficult to increase the molecular weight of the resin containing polyimide bonds.
なお、(a)成分として前記式(2)で示される化合物、(b)成分として化合物(b−1)を用いた場合、次の式(11): When the compound represented by the formula (2) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (11):
また、(a)成分として前記式(5)で示される化合物、(b)成分として化合物(b−1)を用いた場合、次の式(12): When the compound represented by the formula (5) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (12):
また、(a)成分として前記式(6)で示される化合物、(b)成分として化合物(b−1)を用いた場合、次の式(13): When the compound represented by the above formula (6) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (13):
本発明において、(A)成分として使用される「酸無水物基及び/又はカルボキシル基を有する樹脂」の製造方法における(a)成分:酸無水物基を有する三価のポリカルボン酸及びその誘導体、並びに酸無水物基を有する4価のポリカルボン酸から選ばれる1種以上の化合物と、(b)成分:イソシアネート化合物又はアミン化合物との反応は、有機溶媒、好ましくは非含窒素系極性溶媒の存在下に、遊離発生してくる炭酸ガスを反応系より除去しながら加熱縮合させることにより行うことができる。 In the present invention, component (a) in the process for producing “resin having an acid anhydride group and / or carboxyl group” used as component (A): a trivalent polycarboxylic acid having an acid anhydride group and derivatives thereof , And one or more compounds selected from tetravalent polycarboxylic acids having an acid anhydride group and the component (b): an isocyanate compound or an amine compound is an organic solvent, preferably a non-nitrogen-containing polar solvent In the presence of, it can be carried out by heating and condensing while removing carbon dioxide gas generated free from the reaction system.
上記非含窒素系極性溶媒としては、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテルなどのエーテル系溶媒;ジメチルスルホキシド、ジエチルスルホキシド、ジメチルスルホン、スルホランなどの含硫黄系溶媒;γ−ブチロラクトン、酢酸セロソルブなどのエステル系溶媒;シクロヘキサノン、メチルエチルケトンなどのケトン系溶媒;トルエン、キシレンなどの芳香族炭化水素系溶媒、等が挙げられ、これらは単独で又は2種類以上組み合わせて使用することができる。 Examples of the non-nitrogen-containing polar solvent include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, and sulfolane; Examples thereof include ester solvents such as γ-butyrolactone and cellosolve acetate; ketone solvents such as cyclohexanone and methyl ethyl ketone; aromatic hydrocarbon solvents such as toluene and xylene. These may be used alone or in combination of two or more. be able to.
上記溶媒の内から生成する樹脂を溶解する溶剤を選択して使用するのが好ましい。合成後、そのままペーストの溶媒として好適なものを使用することが好ましい。高揮発性であって、低温硬化性を付与でき、かつ効率良く均一系で反応を行うためには、γ−ブチロラクトンが最も好ましい。 It is preferable to select and use a solvent that dissolves the resin produced from the above solvents. After the synthesis, it is preferable to use a suitable paste solvent as it is. Γ-Butyrolactone is the most preferable because it is highly volatile, can impart low-temperature curability, and reacts efficiently in a homogeneous system.
また、溶媒の使用量は、生成するイミド結合を含む樹脂の0.8〜5.0倍(重量比)とすることが好ましい。0.8倍未満では、合成時の粘度が高すぎて、攪拌不能により合成が困難となる傾向があり、5.0倍を超えると、反応速度が低下する傾向がある。 Moreover, it is preferable that the usage-amount of a solvent shall be 0.8-5.0 times (weight ratio) of resin containing the imide bond to produce | generate. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and the synthesis tends to be difficult due to the inability to stir. If it exceeds 5.0 times, the reaction rate tends to decrease.
反応温度は、80〜210℃とすることが好ましく、100〜190℃とすることがより好ましく、120〜180℃とすることが特に好ましい。80℃未満では反応時間が長くなり過ぎ、210℃を超えると反応中に三次元化反応が生じてゲル化が起こり易い。反応時間は、バッチの規模、採用される反応条件により適宜選択することができる。 The reaction temperature is preferably 80 to 210 ° C, more preferably 100 to 190 ° C, and particularly preferably 120 to 180 ° C. If it is less than 80 ° C., the reaction time becomes too long, and if it exceeds 210 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.
また、必要に応じて、三級アミン類、アルカリ金属、アルカリ土類金属、スズ、亜鉛、チタニウム、コバルト等の金属又は半金属化合物等の触媒存在下に反応を行っても良い。 If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
前述のように得られるポリアミド樹脂、ポリアミドイミド樹脂及びポリイミド樹脂は、イソシアネート残基を有するものであり、前記イソシアネート残基を前記一般式(2)及び/又は前記一般式(3)の化合物で反応させることにより、酸無水物基を有する樹脂を得ることができ、後述の(B)成分であるエポキシ樹脂との反応性が向上し、ポリイミド基材への貼り付き性を低減できる。 The polyamide resin, polyamideimide resin and polyimide resin obtained as described above have an isocyanate residue, and the isocyanate residue is reacted with the compound of the general formula (2) and / or the general formula (3). By making it, the resin which has an acid anhydride group can be obtained, the reactivity with the epoxy resin which is the below-mentioned (B) component improves, and the sticking property to a polyimide base material can be reduced.
また、前記一般式(2)及び/又は前記一般式(3)の化合物以外に、本発明の効果を損ねない程度にアルコール類、ラクタム類、オキシム類等のブロック剤を併用することもできる。 In addition to the compounds of the general formula (2) and / or the general formula (3), blocking agents such as alcohols, lactams, and oximes can be used in combination so as not to impair the effects of the present invention.
前記一般式(2)及び/又は前記一般式(3)の化合物としては、下記式(14)で示されるテトラカルボン酸二水物(無水ピロメリット酸)が好ましい。 As the compound of the general formula (2) and / or the general formula (3), a tetracarboxylic acid dihydrate (pyromellitic anhydride) represented by the following formula (14) is preferable.
上記無水ピロメリット酸の添加量は全イソシアネート量に対し、10〜20%の範囲内である。添加量が20%以上であると粘度制御が困難となり、作業性が低下する。また、10%未満では、硬化後にポリイミドフィルムとの貼り付きが生じやすい。 The amount of pyromellitic anhydride added is in the range of 10 to 20% with respect to the total amount of isocyanate. When the addition amount is 20% or more, it is difficult to control the viscosity, and workability is deteriorated. If it is less than 10%, sticking to the polyimide film tends to occur after curing.
また、本発明において、(A)成分として使用できる酸無水物基及び/又はカルボキシル基を有する樹脂のその他のものとしては、例えば、一般式(9)、一般式(10)及び下記一般式(15)を混合し、前記(b−1)を合成する時と同様の条件で反応させて得ることができる。このようにして得られる樹脂は、下記一般式(16)で表される繰り返し構造を含むカルボキシル基を有するウレタン樹脂であり、後述の(B)成分であるエポキシ樹脂との反応性が向上し、ポリイミド基材への貼り付き性を低減できる。
前記のようにして得られるカルボキシル基を有するウレタン樹脂は、イソシアネート残基を有する場合、前記イソシアネート残基を一般式(2)、一般式(3)、アルコール類、ラクタム、オキシム類等を用いて反応させても良い。
一般式(15)で表される化合物としては、例えば、ジメチロールプロピオン酸、ジメチロールブタン酸等が挙げられる。In the present invention, examples of other resins having an acid anhydride group and / or a carboxyl group that can be used as the component (A) include, for example, the general formula (9), the general formula (10), and the following general formula ( 15) can be mixed and reacted under the same conditions as in the synthesis of (b-1). The resin thus obtained is a urethane resin having a carboxyl group containing a repeating structure represented by the following general formula (16), and the reactivity with an epoxy resin which is a component (B) described later is improved. The sticking property to a polyimide base material can be reduced.
When the urethane resin having a carboxyl group obtained as described above has an isocyanate residue, the isocyanate residue is represented by General Formula (2), General Formula (3), alcohols, lactams, oximes and the like. You may make it react.
Examples of the compound represented by the general formula (15) include dimethylolpropionic acid and dimethylolbutanoic acid.
このようにして得られた樹脂の数平均分子量は、15,000〜50,000であることが好ましく、20,000〜45,000であることがより好ましく、25,000〜40,000であることが特に好ましく、その時の分散度は1.5〜3.5が好ましく、2.0〜3.0がより好ましい。数平均分子量が15,000未満であると、硬化被膜とポリイミドフィルムとの貼り付きが生じやすい傾向にあり、数平均分子量が50,000を超えると、樹脂の粘性が高くなり、無機フィラー及び/又は有機フィラーの混合性やスクリーン印刷等の作業性が低下する傾向があるので、好ましくない。 The number average molecular weight of the resin thus obtained is preferably 15,000 to 50,000, more preferably 20,000 to 45,000, and 25,000 to 40,000. It is particularly preferred that the degree of dispersion at that time is preferably 1.5 to 3.5, more preferably 2.0 to 3.0. When the number average molecular weight is less than 15,000, the cured film and the polyimide film tend to stick to each other. When the number average molecular weight exceeds 50,000, the viscosity of the resin increases, and the inorganic filler and / or Alternatively, it is not preferable because workability such as mixing of organic fillers and screen printing tends to deteriorate.
((B)成分:エポキシ樹脂)
本発明の樹脂組成物において、熱硬化性を向上させるために各種エポキシ樹脂を添加する。硬化剤としてのエポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂(油化シェルエポキシ(株)製の商品名「エピコート828」等)、ビスフェノールF型エポキシ樹脂(東都化成(株)製の商品名「YDF−170」等)、フェノールノボラック型エポキシ樹脂(油化シェルエポキシ(株)製の商品名「エピコート152、154」;日本化薬(株)製の商品名「EPPN−201」;ダウケミカル社製の商品名「DEN−438」等)、o−クレゾールノボラック型エポキシ樹脂(日本化薬(株)製の商品名「EOCN−125S,103S,104S」等)、多官能エポキシ樹脂(油化シェルエポキシ(株)製の商品名「Epon1031S」;チバ・スペシャルティ・ケミカルズ(株)製の商品名「アラルダイト0163」;ナガセ化成(株)製の商品名「デナコールEX−611,EX−614,EX−614B,EX−622,EX−512,EX−521,EX−421,EX−411,EX−321」等)、アミン型エポキシ樹脂(油化シェルエポキシ(株)製の商品名「エピコート604」;東都化成(株)製の商品名「YH434」;三菱ガス化学(株)製の商品名「TETRAD−X」、「TERRAD−C」;日本化薬(株)製の商品名「GAN」;住友化学(株)製の商品名「ELM−120」等)、複素環含有エポキシ樹脂(チバ・スペシャルティ・ケミカルズ(株)製の商品名「アラルダイトPT810」等)、脂環式エポキシ樹脂(UCC社製の「ERL4234,4299,4221,4206」等)等が挙げられ、これらを単独で又は2種類以上組合せて使用することができる。これらのエポキシ樹脂のうち、1分子中にエポキシ基を3個以上有するアミン型エポキシ樹脂は、耐溶剤性、耐薬品性、耐湿性の向上の点で特に好ましい。((B) component: epoxy resin)
In the resin composition of the present invention, various epoxy resins are added to improve thermosetting. Examples of the epoxy resin as the curing agent include bisphenol A type epoxy resin (trade name “Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.) and bisphenol F type epoxy resin (trade name manufactured by Toto Kasei Co., Ltd.). “YDF-170” and the like, phenol novolac type epoxy resin (trade name “Epicoat 152, 154” manufactured by Yuka Shell Epoxy Co., Ltd.); product name “EPPN-201” manufactured by Nippon Kayaku Co., Ltd .; Dow Chemical Company name “DEN-438”, etc.), o-cresol novolac type epoxy resin (Nippon Kayaku Co., Ltd. product name “EOCN-125S, 103S, 104S”, etc.), polyfunctional epoxy resin (oilification) Product name “Epon1031S” manufactured by Shell Epoxy Co., Ltd. Product name “Araldite 01 manufactured by Ciba Specialty Chemicals Co., Ltd.” 3 "; trade name" Denacol EX-611, EX-614, EX-614B, EX-622B, EX-512, EX-521, EX-421, EX-411, EX-321 "manufactured by Nagase Kasei Co., Ltd. Etc.), amine type epoxy resin (trade name “Epicoat 604” manufactured by Yuka Shell Epoxy Co., Ltd.); product name “YH434” manufactured by Tohto Kasei Co., Ltd .; product name “TETRAD-” manufactured by Mitsubishi Gas Chemical Co., Ltd. X ”,“ TERRAD-C ”; trade name“ GAN ”manufactured by Nippon Kayaku Co., Ltd .; trade name“ ELM-120 ”manufactured by Sumitomo Chemical Co., Ltd.), heterocycle-containing epoxy resin (Ciba Specialty) Chemicals Co., Ltd. trade name “Araldite PT810”, etc.), alicyclic epoxy resins (UCL “ERL4234, 4299, 4221, 4206” etc.), etc. In or in combination of two kinds or more may be used. Among these epoxy resins, amine-type epoxy resins having 3 or more epoxy groups in one molecule are particularly preferable in terms of improving solvent resistance, chemical resistance, and moisture resistance.
これらのエポキシ樹脂は、1分子中にエポキシ基を1個だけ有するエポキシ化合物を含んでいてもよい。このようなエポキシ化合物は、(A)成分である「イミド結合を含む樹脂」全量に対して0〜20重量%の範囲で使用することが好ましい。このようなエポキシ化合物としては、n−ブチルグリシジルエーテル、フェニルグリシジルエーテル、ジブロモフェニルグシジルエーテル、ジブロモクレジルグリシジルエーテル等がある。また、3,4−エポキシシクロヘキシル、メチル(3,4−エポキシシクロヘキサン)カルボキシレート等の脂環式エポキシ化合物を使用することができる。 These epoxy resins may contain an epoxy compound having only one epoxy group in one molecule. Such an epoxy compound is preferably used in the range of 0 to 20% by weight based on the total amount of the “resin containing an imide bond” as the component (A). Examples of such an epoxy compound include n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, and dibromocresyl glycidyl ether. In addition, alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate can be used.
これらのエポキシ樹脂の使用量は、(A)成分として用いる「酸無水物基及び/又はカルボキシル基を有する樹脂」100重量部に対して、好ましくは1〜50重量部、より好ましくは2〜45重量部、さらに好ましくは3〜40重量部とされる。エポキシ樹脂の配合量が1重量部未満では、樹脂組成物の硬化性、耐溶剤性、耐薬品性、耐湿性が低下する傾向にあり、50重量部を超えると、耐熱性及び粘度安定性が低下する傾向にある。 The amount of these epoxy resins used is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts per 100 parts by weight of “resin having acid anhydride group and / or carboxyl group” used as component (A). Part by weight, more preferably 3 to 40 parts by weight. When the compounding amount of the epoxy resin is less than 1 part by weight, the curability, solvent resistance, chemical resistance, and moisture resistance of the resin composition tend to decrease. When the amount exceeds 50 parts by weight, the heat resistance and viscosity stability are increased. It tends to decrease.
上記エポキシ樹脂の添加方法としては、添加するエポキシ樹脂を(A)成分として用いる「酸無水物基及び/又はカルボキシル基を有する樹脂」を溶解する有機溶剤と同一の有機溶剤に溶解してから添加してもよく、また、直接添加してもよい。 As the method for adding the epoxy resin, the epoxy resin to be added is used after being dissolved in the same organic solvent as the organic solvent for dissolving the “resin having an acid anhydride group and / or carboxyl group” as the component (A). It may also be added directly.
〔(C)成分:ハイドロタルサイトを含むフィラー〕
本発明における(C)成分として用いられるフィラーは、ハイドロタルサイトを含むものである。本発明の樹脂組成物に用いる(C)成分は、ハイドロタルサイトを必須成分として含有するフィラーである。このフィラーの含有量は、前記(A)成分100重量部に対して、1〜250重量部とすることが好ましく、30〜200重量部とすることがより好ましく、50〜100重量部とすることが特に好ましい。この(C)成分の含有量がこれよりも少ない場合、樹脂組成物ペーストの粘度及びチキソトロピー係数が低くなり、ペーストの糸引きが増加するとともに印刷後のペーストの流れ出しが大きくなり、樹脂組成物の膜厚も薄膜化する傾向があり、硬化被膜の電気特性が劣る傾向になる。また、(C)成分の含有量がこれより多い場合、樹脂組成物ペーストの粘度及びチキソトロピー係数が高くなり、ペーストの基材への転写性が低下するとともに印刷膜中のボイド及びピンホールが増加する傾向となる。[(C) component: filler containing hydrotalcite]
The filler used as the component (C) in the present invention contains hydrotalcite. Component (C) used in the resin composition of the present invention is a filler containing hydrotalcite as an essential component. The content of the filler is preferably 1 to 250 parts by weight, more preferably 30 to 200 parts by weight, and more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the component (A). Is particularly preferred. When the content of the component (C) is less than this, the viscosity and thixotropy coefficient of the resin composition paste are lowered, the stringing of the paste is increased, and the flow of the paste after printing is increased. The film thickness also tends to be reduced, and the electrical properties of the cured film tend to be inferior. In addition, when the content of component (C) is higher than this, the viscosity and thixotropy coefficient of the resin composition paste are increased, the transferability of the paste to the substrate is lowered, and voids and pinholes in the printed film are increased. Tend to.
((C)成分の粒径)
本発明の樹脂組成物に用いる(C)成分:フィラーは、平均粒子径50μm以下、最大粒子径100μm以下の粒子径であることが好ましく用いられる。平均粒子径が50μmを超えると、後述するチキソトロピー係数が1.1以上の樹脂組成物ペーストが得られにくくなり、最大粒子径が100μmを超えると、樹脂組成物の塗膜の外観、密着性が不十分となる傾向がある。この(C)成分の平均粒子径は、より好ましくは、30μm以下、さらに好ましくは10μm以下、特に好ましくは1μm以下である。また、この(C)成分の最大粒子径は、より好ましくは80μm以下、さらに好ましくは60μm以下、特に好ましくは40μm以下である。(Particle size of component (C))
Component (C) used in the resin composition of the present invention: The filler is preferably used with an average particle size of 50 μm or less and a maximum particle size of 100 μm or less. When the average particle diameter exceeds 50 μm, it becomes difficult to obtain a resin composition paste having a thixotropic coefficient of 1.1 or more, which will be described later. When the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film of the resin composition are There is a tendency to become insufficient. The average particle size of the component (C) is more preferably 30 μm or less, further preferably 10 μm or less, and particularly preferably 1 μm or less. Further, the maximum particle size of the component (C) is more preferably 80 μm or less, further preferably 60 μm or less, and particularly preferably 40 μm or less.
(ハイドロタルサイト)
ハイドロタルサイト(hydrotalcite)は、下記一般式(17)で表される復水酸化物である。
M1 8−xM2 x(OH)16CO3・nH2O (17)
(式(17)中、M1は、Mg2+、Fe2+、Zn2+、Ca2+、Li2+、Ni2+、Co2+、Cu2+を示し、M2は、Al3+、Fe3+、Mn3+を示し、xは2〜5の整数を示し、nは正の整数を示す。)
これらの中でも、下記の化学組成式で表されるマグネシウムとアルミニウムの化合物が特に好ましく、HT−P(堺化学株式会社製、商品名)として商業的に入手可能である。
Mg6Al2(OH)16CO3・4H2O(Hydrotalcite)
Hydrotalcite is a condensed hydroxide represented by the following general formula (17).
M 1 8-x M 2 x (OH) 16 CO 3 .nH 2 O (17)
(In Formula (17), M 1 represents Mg 2+ , Fe 2+ , Zn 2+ , Ca 2+ , Li 2+ , Ni 2+ , Co 2+ , Cu 2+ , and M 2 represents Al 3+ , Fe 3+ , Mn 3+ . X represents an integer of 2 to 5, and n represents a positive integer.)
Among these, the compound of magnesium and aluminum represented by the following chemical composition formula is particularly preferable, and is commercially available as HT-P (trade name, manufactured by Sakai Chemical Co., Ltd.).
Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O
本発明の樹脂組成物に添加するフィラーの成分としてハイドロタルサイトは、制酸剤の作用があり、酸無水物基及び/又はカルボキシル基を有する樹脂を含む樹脂組成物の増粘を軽減できる効果がある。また、ハイドロタルサイトは、炭酸基が解離して炭酸イオン(CO3 2−)を生成し、この炭酸イオンが樹脂組成物中に含まれる塩化物イオン(Cl−)及び/又は硫酸イオン(SO4 −)と置換する作用を有している。塩化物イオン(Cl−)及び/又は硫酸イオン(SO4 −)が硬化被膜中に存在すると絶縁信頼性に悪影響を及ぼすが、前記炭酸イオンとの置換作用により絶縁信頼性を向上することができる。しかし、過剰な配合量は印刷外観上不具合を生じ、好ましくない。さらに、本発明の樹脂組成物にハイドロタルサイトを配合することにより、本発明の樹脂組成物の硬化被膜により保護した配線板において、通電後の電極の黒膨れを軽減することができるという効果が得られる。また、ハイドロタルサイトは、難燃性を良好にできるという効果も得られる。Hydrotalcite as a filler component added to the resin composition of the present invention has the effect of an antacid and can reduce the thickening of a resin composition containing a resin having an acid anhydride group and / or a carboxyl group There is. Hydrotalcite dissociates carbonate groups to generate carbonate ions (CO 3 2− ), and the carbonate ions are contained in the resin composition chloride ions (Cl − ) and / or sulfate ions (SO 2). 4 -) and it has the effect of substitution. When chloride ions (Cl − ) and / or sulfate ions (SO 4 − ) are present in the cured coating, the insulation reliability is adversely affected, but the insulation reliability can be improved by the substitution action with the carbonate ions. . However, an excessive blending amount is not preferable because it causes problems in printing appearance. Furthermore, by blending hydrotalcite with the resin composition of the present invention, in the wiring board protected by the cured film of the resin composition of the present invention, there is an effect that the black swelling of the electrode after energization can be reduced. can get. Hydrotalcite also has the effect of improving the flame retardancy.
このハイドロタルサイトの含有量は、(A)成分100重量部に対して1〜50重量部とすることが好ましく、5〜40重量部とすることがより好ましく、10〜30重量部とすることが特に好ましい。ハイドロタルサイトの含有量が1重量部未満となると、樹脂組成物の増粘軽減効果が不十分になる、及び電極の黒膨れが発生する傾向があり、50重量部以上では樹脂組成物の印刷外観の不具合などの影響がでてくる傾向がある。 The hydrotalcite content is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of component (A). Is particularly preferred. If the hydrotalcite content is less than 1 part by weight, the effect of reducing the thickening of the resin composition tends to be insufficient, and black swelling of the electrode tends to occur. There is a tendency for the appearance to be affected.
また、ハイドロタルサイトの(C)成分中の含有量は、10質量%〜50質量%であることが好ましく、10〜30質量%であることがより好ましく、15〜25質量%であることが特に好ましい。(C)成分中のハイドロタルサイトの含有量が10質量%未満となると、樹脂組成物の増粘軽減効果が不十分となり、50質量%を超えると、樹脂組成物の印刷外観の不具合などの影響がでてくる。 The content of the hydrotalcite in the component (C) is preferably 10% by mass to 50% by mass, more preferably 10-30% by mass, and 15-25% by mass. Particularly preferred. When the content of hydrotalcite in the component (C) is less than 10% by mass, the effect of reducing the increase in the viscosity of the resin composition becomes insufficient. When the content exceeds 50% by mass, the printed appearance of the resin composition is not satisfactory. The effect will come out.
本発明に用いる(C)成分におけるハイドロタルサイト以外のフィラー成分としては、無機フィラーおよび/または有機フィラーを用いることができる。まず、無機フィラーについて説明する。 As the filler component other than hydrotalcite in the component (C) used in the present invention, an inorganic filler and / or an organic filler can be used. First, the inorganic filler will be described.
ハイドロタルサイトは前述のように無機フィラーの一種であるが、このハイドロタルサイト以外の無機フィラーとしては、例えば、シリカ(SiO2)、アルミナ(Al2O3)、チタニア(TiO2)、酸化タンタル(Ta2O5)、ジルコニア(ZrO2)、窒化ケイ素(Si3N4)、チタン酸バリウム(BaO・TiO2)、炭酸バリウム(BaCO3)、チタン酸鉛(PbO・TiO2)、チタン酸ジルコン酸鉛(PZT)、チタン酸ジルコン酸ランタン鉛(PLZT)、酸化ガリウム(Ga2O3)、スピネル(MgO・Al2O3)、ムライト(3Al2O3・2SiO2)、コーディエライト(2MgO・2Al2O3/5SiO2)、タルク(3MgO・4SiO2・H2O)、チタン酸アルミニウム(TiO2−Al2O3)、イットリア含有ジルコニア(Y2O3−ZrO2)、ケイ酸バリウム(BaO・8SiO2)、窒化ホウ素(BN)、炭酸カルシウム(CaCO3)、硫酸カルシウム(CaSO4)、酸化亜鉛(ZnO)、チタン酸マグネシウム(MgO・TiO2)、硫酸バリウム(BaSO4)、有機ベントナイト、カーボン(C)等を使用することができ、これらの1種又は2種以上を使用することもできる。As described above, hydrotalcite is a kind of inorganic filler. Examples of inorganic fillers other than hydrotalcite include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), and oxidation. Tantalum (Ta 2 O 5 ), zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO · TiO 2 ), barium carbonate (BaCO 3 ), lead titanate (PbO · TiO 2 ), Lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O 3 ), spinel (MgO · Al 2 O 3 ), mullite (3Al 2 O 3 · 2SiO 2 ), Cody Eraito (2MgO · 2Al 2 O 3 / 5SiO 2), talc (3MgO · 4SiO 2 · H 2 O), aluminum titanate (TiO 2 -Al 2 O 3), yttria-containing zirconia (Y 2 O 3 -ZrO 2) , barium silicate (BaO · 8SiO 2), boron nitride (BN), calcium carbonate (CaCO 3), calcium sulfate (CaSO 4), zinc oxide (ZnO ), Magnesium titanate (MgO · TiO 2 ), barium sulfate (BaSO 4 ), organic bentonite, carbon (C), and the like, and one or more of these can also be used.
これら無機フィラーの中でも特に、電気特性(絶縁信頼性等)をも良好にできる観点から、硫酸バリウム、タルクを用いることが好ましい。また、印刷性、作業性の観点から硫酸バリウムを用いることが好ましい。 Among these inorganic fillers, barium sulfate and talc are preferably used from the viewpoint of improving electrical characteristics (insulation reliability and the like). Moreover, it is preferable to use barium sulfate from a viewpoint of printability and workability.
一方の有機フィラーとしては、アミド結合、イミド結合、エステル結合又はエーテル結合を有する耐熱性樹脂の微粒子が好ましい。このような耐熱性樹脂としては、耐熱性と機械特性の観点から好ましくはポリイミド樹脂若しくはその前駆体、ポリアミドイミド樹脂若しくはその前駆体、又はポリアミド樹脂の微粒子が用いられる。 One organic filler is preferably heat-resistant resin fine particles having an amide bond, an imide bond, an ester bond or an ether bond. As such a heat-resistant resin, polyimide resin or a precursor thereof, polyamideimide resin or a precursor thereof, or fine particles of polyamide resin are preferably used from the viewpoint of heat resistance and mechanical properties.
上記有機フィラーとして用いられる耐熱性樹脂は、以下のようにして製造することができる。
まず、上記耐熱性樹脂の一つであるポリイミド樹脂は、(c)芳香族テトラカルボン酸二無水物と(d)芳香族ジアミン化合物とを反応させて得ることができる。The heat resistant resin used as the organic filler can be produced as follows.
First, a polyimide resin which is one of the above heat-resistant resins can be obtained by reacting (c) an aromatic tetracarboxylic dianhydride and (d) an aromatic diamine compound.
(c)芳香族テトラカルボン酸二無水物としては、例えば、無水ピロメリット酸、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、2,2’,3,3’−ビスフェニルテトラカルボン酸二無水物、2,2’,3,3’−ビフェニルテトラカルボン酸二無水物、2,3,3’,4’−ビフェニルテトラカルボン酸二無水物、2,2−ビス(3,4−ジカルボキシフェニル)プロパン二無水物、1,1−ビス(3,4−ジカルボキシフェニル)エタン二無水物、ビス(2,3−ジカルボキシフェニル)メタン二無水物、ビス(3,4−ジカルボキシフェニル)メタン二無水物、ビス(3,4−ジカルボキシフェニル)スルホン二無水物、3,4,9,10−ペリレンテトラカルボン酸二無水物、ビス(3,4−ジカルボキシフェニル)エーテル二無水物、ベンゼン−1,2,3,4−テトラカルボン酸二無水物、3,4,3’,4’−ベンゾフェノンテトラカルボン酸二無水物、2,3,2’,3’−ベンゾフェノンテトラカルボン酸二無水物、2,3,3’,4’−ベンゾフェノンテトラカルボン酸二無水物、1,2,5,6−ナフタレンテトラカルボン酸二無水物、2,3,6,7−ナフタレンテトラカルボン酸二無水物、1,2,4,5−ナフタレンテトラカルボン酸二無水物、1,4,5,8−ナフタレンテトラカルボン酸二無水物、2,6−ジクロルナフタレン−1,4,5,8−テトラカルボン酸二無水物、2,7−ジクロルナフタレン−1,4,5,8−テトラカルボン酸二無水物、2,3,6,7−テロラクロルナフタレン−1,4,5,8−テトラカルボン酸二無水物、フェナンスレン−1,8,9,10−テトラカルボン酸二無水物、ビス(3,4−ジカルボキシフェニル)ジメチルシラン二無水物、ビス(3,4−ジカルボキシフェニル)メチルフェニルシラン二無水物、ビス(3,4−ジカルボキシフェニル)ジフェニルシラン二無水物、1,4−ビス(3,4−ジカルボキシフェニルジメチルシリル)ベンゼン二無水物、1,3−ビス(3,4−ジカルボキシフェニル)−1,1,3,3−テトラメチルジシクロヘキサン二無水物、p−フェニレンビス(トリメリット酸モノエステル酸無水物)、2,2−ビス(3,4−ジカルボキシフェニル)ヘキサフルオロプロパン二無水物、2,2−ビス{4−(3,4−ジカルボキシフェノキシ)フェニル}ヘキサフルオロプロパン二無水物、2,2−ビス{4−(3,4−ジカルボキシフェノキシ)フェニル}プロパン二無水物、4,4−ビス(3,4−ジカルボキシフェノキシ)ジフェニルスルフィド二無水物、1,4−ビス(2−ヒドロキシヘキサフルオロイソプロピル)ベンゼンビス(トリメリテート無水物)、1,3−ビス(2−ヒドロキシヘキサフルオロイソプロピル)ベンゼンビス(トリメリテート無水物)、1,2−(エチレン)ビス(トリメリテート無水物)、1,3−(トリメチレン)ビス(トリメリテート無水物)、1,4−(テトラメチレン)ビス(トリメリテート無水物)、1,5−(ペンタメチレン)ビス(トリメリテート無水物)、1,6−(ヘキサメチレン)ビス(トリメリテート無水物)、1,7−(ヘプタメチレン)ビス(トリメリテート無水物)、1,8−(オクタメチレン)ビス(トリメリテート無水物)、1,9−(ノナメチレン)ビス(トリメリテート無水物)、1,10−(デカメチレン)ビス(トリメリテート無水物)、1,12−(ドデカメチレン)ビス(トリメリテート無水物)、1,16−(ヘキサデカメチレン)ビス(トリメリテート無水物)、1,18−(オクタデカメチレン)ビス(トリメリテート無水物)等が挙げられ、これらを混合して用いてもよい。 (C) As aromatic tetracarboxylic dianhydride, for example, pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-bis Phenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3 , 4-Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-di Carboxyphenyl Ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′- Benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1, 4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-terolachlornaphthalene-1, 4,5,8-tetracar Acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methyl Phenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3 , 4-Dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 2,2-bis (3,4-di Carboxyphenyl) hexafluoropropane dianhydride, 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropane dianhydride, 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis ( 2-hydroxyhexafluoroisopropyl) benzene bis (trimellitate anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitate anhydride), 1,2- (ethylene) bis (trimellitate anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexa Methylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitate anhydrous) ), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- ( Dodecamemethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), and the like. May be used.
上記(c)芳香族テトラカルボン酸二無水物には、目的に応じて芳香族テトラカルボン酸二無水物以外のテトラカルボン酸二無水物を、芳香族テトラカルボン酸二無水物の50モル%を超えない範囲で用いることができる。このようなテトラカルボン酸二無水物としては、例えば、エチレンテトラカルボン酸二無水物、1,2,3,4−ブタンテトラカルボン酸二無水物、ピラジン−2,3,5,6−テトラカルボン酸二無水物、チオフェン−2,3,4,5−テトラカルボン酸二無水物、デカヒドロナフタレン−1,4,5,8−テトラカルボン酸二無水物、4,8−ジメチル−1,2,3,5,6,7−ヘキサヒドロナフタレン−1,2,5,6−テトラカルボン酸二無水物、シクロペンタン−1,2,3,4−テトラカルボン酸二無水物、ピロリジン−2,3,4,5−テトラカルボン酸二無水物、1,2,3,4−シクロブタンテトラカルボン酸二無水物、ビス{エキソービシクロ〔2,2,1〕ヘプタン−2,3−ジカルボン酸無水物}スルホン、ビシクロ−(2,2,2)−オクト(7)−エン−2,3,5,6−テトラカルボン酸二無水物、5−(2,5−ジオキソテトラヒドロフリル)−3−メチル−3−シクロヘキサン−1,2−ジカルボン酸無水物、テトラヒドロフラン−2,3,4,5−テトラカルボン酸二無水物等が挙げられる。 In the above (c) aromatic tetracarboxylic dianhydride, a tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride is added according to the purpose, and 50 mol% of the aromatic tetracarboxylic dianhydride is added. It can be used within a range not exceeding. Examples of such tetracarboxylic dianhydrides include ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic Acid dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2 , 3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2, 3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis {exobicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride Thing} sulfone, bishi Rho- (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3 -Cyclohexane-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and the like.
次に、上記(d)芳香族ジアミン化合物としては、例えば、o−フェニレンジアミン、m−フェニレンジアミン、p−フェニレンジアミン、3,3’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルエーテル、3,4’−ジアミノジフェニルエーテル、3,3’−ジアミノジフェニルメタン、3,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルメタン、3,3’−ジアミノジフェニルジフルオロメタン、4,4’−ジアミノジフェニルジフルオロメタン、3,3’−ジアミノジフェニルスルホン、3,4’−ジアミノジフェニルスルホン、4,4’−ジアミノジフェニルスルホン、3,3’−ジアミノジフェニルスルフィド、3,3’−ジアミノジフェニルケトン、3,4’−ジアミノジフェニルケトン、4,4’−ジアミノジフェニルケトン、2,2−ビス(3−アミノフェニル)プロパン、2,2−ビス(3,4′−ジアミノフェニル)プロパン、2,2−ビス(4−アミノフェニル)プロパン、2,2−ビス(3−アミノフェニル)ヘキサフルオロプロパン、2,2−ビス(3,4’−ジアミノフェニル)ヘキサフルオロプロパン、2,2−ビス(4−アミノフェニル)ヘキサフルオロプロパン、1,3−ビス(3−アミノフェニル)ベンゼン、1,4−ビス(4−アミノフェニル)ベンゼン、3,3’−〔1,4−フェニレンビス(1−メチルエチリデン)〕ビスアニリン、3,4’−〔1,4−フェニレンビス(1−メチルエチリデン)〕ビスアニリン、4,4’−〔1,4−フェニレンビス(1−メチルエチリデン)〕ビスアニリン、2,2−ビス〔4−(3−アミノフェノキシ)フェニル〕プロパン、2,2−ビス〔4−(4−アミノフェノキシ)フェニル〕プロパン、2,2−ビス〔4−(3−アミノフェノキシ)フェニル〕ヘキサフルオプロパン、2,2−ビス〔4−(4−アミノフェノキシ)フェニル〕ヘキサフルオロプロパン、ビス〔4−(3−アミノフェノキシ)フェニル〕スルフィド、ビス〔4−(4−アミノフェノキシ)フェニル〕スルフィド、ビス〔4−(3−アミノフェノキシ)フェニル〕スルホン、ビス〔4−(4−アミノフェノキシ)フェニル〕スルホン等が挙げられ、これらを混合して用いてもよい。 Next, as the above (d) aromatic diamine compound, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3, , 3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diamino Diphenyl ketone, , 4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2-bis (3,4'-diaminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3,4'-diaminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1, 3-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 3,3 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,4′- [1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) Phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, and the like. These may be used in combination.
上記(d)芳香族ジアミン化合物には、目的に応じて芳香族ジアミン化合物以外のジアミン化合物を芳香族ジアミン化合物の50モル%を超えない範囲で用いることができる。このようなジアミン化合物としては、例えば、1,2−ジアミノエタン、1,3−ジアミノプロパン、1,4−ジアミノブタン、1,5−ジアミノペンタン、1,6−ジアミノヘキサン、1,7−ジアミノヘプタン、1,8−ジアミノオクタン、1,9−ジアミノノナン、1,10−ジアミノデカン、1,11−ジアミノウンデカン、1,3−ビス(3−アミノプロピル)テトラメチルジシロキサン、1,3−ビス(3−アミノプロピル)テトラメチルポリシロキサン等が挙げられる。 In the (d) aromatic diamine compound, a diamine compound other than the aromatic diamine compound can be used in a range not exceeding 50 mol% of the aromatic diamine compound depending on the purpose. Examples of such diamine compounds include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino. Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetramethylpolysiloxane and the like.
上記(c)芳香族テトラカルボン酸二無水物と上記(d)芳香族ジアミン化合物とは、ほぼ等モルで反応させることが、樹脂組成物の膜特性の点で、好ましい。 The (c) aromatic tetracarboxylic dianhydride and the (d) aromatic diamine compound are preferably reacted in an equimolar amount from the viewpoint of the film properties of the resin composition.
(c)芳香族テトラカルボン酸二無水物と(d)芳香族ジアミン化合物との反応は、有機溶媒中で行う。この場合の有機溶媒としては、例えば、N−メチル−2−ピロリドン、ジメチルアセトアミド、ジメチルホルムアミド、1,3−ジメチル−3,4,5,6−テトラヒドロ2(1H)−ピリミジノン、1,3−ジメチル−2−イミダゾリジノン等の含窒素化合物;スルホラン、ジメチルスルホキシド等の硫黄化合物;γ−ブチロラクトン、γ−バレロラクトン、γ−カプロラクトン、γ−ヘプタラクトン、α−アセチル−γ−ブチロラクトン、ε−カプロラクトン等のラクトン類;ジオキサン、1,2−ジメトキシエタン、ジエチレングリコ−ルジメチル(又はジエチル、ジプロピル、ジブチル)エーテル、トリエチレングリコール(又はジエチル、ジプロピル、ジブチル)エーテル、テトラエチレングリコールジメチル(又はジエチル、ジプロピル、ジブチル)エーテル等のエーテル類;メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、アセトフェノン等のケトン類;ブタノール、オクチルアルコール、エチレングリコール、グリセリン、ジエチレングリコールモノメチル(又はモノエチル)エーテル、トリエチレングリコールモノメチル(又はモノエチル)エーテル、テトラエチレングリコールモノメチル(又はモノエチル)エーテル等のアルコール類;フェノール、クレゾール、キシレノール等のフェノール類;酢酸エチル、酢酸ブチル、エチルセロソルブアセテート、ブチルセロソルブアセテート等のエステル類;トルエン、キシレン、ジエチルベンゼン、シクロヘキサン等の炭化水素類;トリクロロエタン、テトタクロロエタン、モノクロロベンゼン等のハロゲン化炭化水素類等が用いられる。これらの有機溶媒は、単独又は混合して用いられる。溶解性、低吸湿性、低温硬化性、環境安全性等を考慮するとラクトン類、エーテル類、ケトン類等を用いることが好ましい。 The reaction between (c) the aromatic tetracarboxylic dianhydride and (d) the aromatic diamine compound is carried out in an organic solvent. Examples of the organic solvent in this case include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3- Nitrogen-containing compounds such as dimethyl-2-imidazolidinone; sulfur compounds such as sulfolane and dimethyl sulfoxide; γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε- Lactones such as caprolactone; dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol (or diethyl, dipropyl, dibutyl) ether, tetraethylene glycol dimethyl (or diethyl, dipro Ethers such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone; butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) Alcohols such as ether and tetraethylene glycol monomethyl (or monoethyl) ether; phenols such as phenol, cresol and xylenol; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate; toluene, xylene, diethylbenzene and cyclohexane Hydrocarbons such as trichloroethane, tetotachloroethane, monochlorobenzene, etc. Rogenated hydrocarbons and the like are used. These organic solvents are used alone or in combination. In consideration of solubility, low hygroscopicity, low temperature curability, environmental safety, etc., it is preferable to use lactones, ethers, ketones and the like.
反応温度は80℃以下、好ましくは0〜50℃で行う。反応が進行するにつれ反応液は徐々に増粘する。この場合、ポリイミド樹脂の前駆体であるポリアミド酸が生成する。このポリアミド酸を部分的にイミド化してもよく、これもポリイミド樹脂の前駆体に含まれる。 The reaction temperature is 80 ° C or lower, preferably 0 to 50 ° C. As the reaction proceeds, the reaction solution gradually thickens. In this case, polyamic acid which is a precursor of the polyimide resin is generated. This polyamic acid may be partially imidized, and this is also included in the polyimide resin precursor.
上記ポリイミド樹脂は、上記反応物(ポリアミド酸)を脱水閉環して得られる。脱水閉環は、120℃〜250℃で熱処理する方法(熱イミド化)や脱水剤を用いて行う方法(化学イミド化)で行うことができる。120℃〜250℃で熱処理する方法の場合、脱水反応で生じる水を系外に除去しながら行うことが好ましい。この際、ベンゼン、トルエン、キシレン等を用いて水を共沸除去してもよい。 The polyimide resin is obtained by dehydrating and ring-closing the reactant (polyamide acid). Dehydration ring closure can be performed by a method of heat treatment at 120 ° C. to 250 ° C. (thermal imidization) or a method of using a dehydrating agent (chemical imidization). In the case of the heat treatment at 120 ° C. to 250 ° C., it is preferable to carry out while removing water generated by the dehydration reaction out of the system. At this time, water may be removed azeotropically using benzene, toluene, xylene or the like.
脱水剤を用いて脱水閉環を行う方法は、脱水剤として無水酢酸、無水プロピオン酸、無水安息香酸等の酸無水物、ジシクロヘキシルカルボジイミド等のカルボジイミド化合物等を用いるのが好ましい。このとき必要に応じてピリジン、イソキノリン、トリメチルアミン、アミノピリジンイミダゾール等の脱水触媒を用いてもよい。脱水剤又は脱水触媒は、芳香族テトラカルボン酸二無水物1モルに対し、それぞれ1〜8モルの範囲で用いることが好ましい。 In the method of performing dehydration and ring closure using a dehydrating agent, it is preferable to use an acid anhydride such as acetic anhydride, propionic anhydride or benzoic acid, a carbodiimide compound such as dicyclohexylcarbodiimide, or the like as the dehydrating agent. At this time, if necessary, a dehydration catalyst such as pyridine, isoquinoline, trimethylamine, or aminopyridineimidazole may be used. The dehydrating agent or the dehydrating catalyst is preferably used in an amount of 1 to 8 moles per mole of aromatic tetracarboxylic dianhydride.
前記ポリアミドイミド樹脂又はその前駆体は、前記ポリイミド樹脂又はその前駆体の製造において、芳香族テトラカルボン酸二無水物の代わりに、トリメリット酸無水物又はトリメリット酸無水物誘導体(トリメリット酸無水物のクロライド等)等の三価のトリカルボン酸無水物又はその誘導体を使用して製造することができる。また、芳香族ジアミン化合物及びその他のジアミン化合物の代わりに、アミノ基以外の残基がそのジアミン化合物に対応するジイソシアネート化合物を使用して製造することもできる。使用できるジイソシアネート化合物としては、前記芳香族ジアミン化合物又はその他のジアミン化合物とホスゲン又は塩化チオニルを反応させて得られるものがある。 The polyamide-imide resin or precursor thereof is trimellitic anhydride or trimellitic anhydride derivative (trimellitic anhydride anhydrous) instead of aromatic tetracarboxylic dianhydride in the production of the polyimide resin or precursor thereof. Trivalent tricarboxylic acid anhydrides or derivatives thereof such as chlorides of the products. Moreover, it can also manufacture using the diisocyanate compound corresponding to the diamine compound in which residues other than an amino group replace with an aromatic diamine compound and another diamine compound. Diisocyanate compounds that can be used include those obtained by reacting the aromatic diamine compound or other diamine compounds with phosgene or thionyl chloride.
前記ポリアミド樹脂は、テレフタル酸、イソフタル酸、フタル酸等の芳香族ジカルボン酸、これらのジクロライド、酸無水物等の誘導体と前記した芳香族ジアミン化合物又はこれと他のジアミン化合物を反応させることにより製造することができる。 The polyamide resin is produced by reacting an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or phthalic acid, a derivative thereof such as dichloride or acid anhydride, and the above-described aromatic diamine compound or another diamine compound. can do.
前記エステル結合を有する耐熱性樹脂としては、例えばポリエステル樹脂が挙げられ、ポリエステル樹脂としては、上記のテレフタル酸、イソフタル酸、フタル酸等の芳香族ジカルボン酸、これらのジクロライド、酸無水物等の誘導体と1,4−ジヒドロキシベンゼン、ビスフェノールF、ビスフェノールA、4,4′−ジヒドロキシビフェニル等の芳香族ジオール化合物を反応させて得られるものがある。 Examples of the heat-resistant resin having an ester bond include a polyester resin. Examples of the polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid, and derivatives such as dichloride and acid anhydride. And an aromatic diol compound such as 1,4-dihydroxybenzene, bisphenol F, bisphenol A, and 4,4'-dihydroxybiphenyl.
また、前記ポリアミドイミド樹脂としては、芳香族テトラカルボン酸二無水物と、イソフタル酸ジヒドラジドを必須成分として含有する芳香族ジアミン化合物とを反応させて得られるポリアミドイミド樹脂が好ましく用いられる。芳香族テトラカルボン酸二無水物及び芳香族ジアミン化合物としては、前記のものが用いられる。イソフタル酸ジヒドラジドの芳香族ジアミン化合物中のモル比は1〜100モル%とすることが好ましい。1モル%未満では変性ポリアミドイミド樹脂に対する耐溶解性が低下する傾向にあり、イソフタル酸ジヒドラジドの含有量が多いと、本発明の樹脂組成物のペーストによって形成される層の耐湿性が低下する傾向にあるので、10〜80モル%がより好ましく、20〜70モル%が特に好ましく用いられる。このポリアミドイミド樹脂は芳香族テトラカルボン酸二無水物と芳香族ジアミン化合物との配合比、使用有機溶媒、合成法等を前記ポリイミド樹脂の合成と同様にして得ることができる。 As the polyamideimide resin, a polyamideimide resin obtained by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine compound containing isophthalic acid dihydrazide as an essential component is preferably used. As the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, those described above are used. The molar ratio of isophthalic acid dihydrazide in the aromatic diamine compound is preferably 1 to 100 mol%. If it is less than 1 mol%, the solubility resistance with respect to the modified polyamideimide resin tends to decrease, and if the content of isophthalic acid dihydrazide is large, the moisture resistance of the layer formed by the paste of the resin composition of the present invention tends to decrease. Therefore, 10 to 80 mol% is more preferable, and 20 to 70 mol% is particularly preferably used. This polyamide-imide resin can be obtained in the same manner as the synthesis of the polyimide resin, with respect to the compounding ratio of the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, the organic solvent used, the synthesis method, and the like.
トリメリット酸無水物及び必要に応じてジカルボン酸とポリイソシアネートを反応させて得られるポリアミドイミド樹脂は、加熱することにより有機溶剤に不溶性になりやすく、このポリアミドイミド樹脂からなる有機微粒子を使用することもできる。このポリアミドイミド樹脂の製造方法については、前記したポリアミドイミド樹脂の製造方法と同様にして製造することができる。 The polyamideimide resin obtained by reacting trimellitic anhydride and, if necessary, dicarboxylic acid and polyisocyanate is likely to become insoluble in organic solvents when heated, and organic fine particles made of this polyamideimide resin should be used. You can also. About the manufacturing method of this polyamideimide resin, it can manufacture similarly to the manufacturing method of an above described polyamideimide resin.
上記樹脂を(C)成分:フィラーとして用いるための微粒子化の方法としては、例えば、非水分散重合法(例えば、特公昭60−48531号公報、特開昭59−230018号公報を参照)、沈殿重合法(例えば、特開昭59−108030号公報、特開昭60−221425号公報を参照)、樹脂溶液から改修した粉末を機械粉砕する方法、樹脂溶液を貧触媒に加えながら高せん断下に微粒子化する方法、樹脂溶液の噴霧溶液を乾燥して微粒子を得る方法、洗剤又は樹脂溶液中で溶剤に対して溶解性の温度依存性を持つ樹脂を析出微粒子化する方法等がある。 Examples of the fine particle method for using the resin as the component (C) as a filler include, for example, a non-aqueous dispersion polymerization method (see, for example, JP-B-60-48531, JP-A-59-230018), Precipitation polymerization method (for example, see JP-A-59-108030 and JP-A-60-221425), a method of mechanically pulverizing powder modified from a resin solution, under high shear while adding the resin solution to a poor catalyst There are a method for making fine particles, a method for obtaining fine particles by drying a spray solution of a resin solution, a method for forming fine particles by precipitation of a resin having a temperature dependency that is soluble in a solvent in a detergent or a resin solution, and the like.
前述したように、本発明に用いる(C)成分:フィラー(ハイドロタルサイトを含有する無機微粒子及び/又は有機微粒子)としては、平均粒子径50μm以下、最大粒子径100μm以下の粒子径をもつものが好ましく用いられる。平均粒子径が50μmを超えると、後述するチキソトロピー係数が1.1以上のペーストが得られにくくなり、最大粒子径が100μmを超えると、樹脂組成物の塗膜の外観、密着性が不十分となる傾向がある。平均粒子径は、より好ましくは、30μm以下、さらに好ましくは10μm以下、特に好ましくは1μm以下であり、最大粒子径はより好ましくは80μm以下、さらに好ましくは60μm以下、特に好ましくは40μm以下である。 As described above, the component (C) used in the present invention: the filler (inorganic fine particles and / or organic fine particles containing hydrotalcite) has an average particle size of 50 μm or less and a maximum particle size of 100 μm or less. Is preferably used. When the average particle diameter exceeds 50 μm, it becomes difficult to obtain a paste having a thixotropic coefficient of 1.1 or more, which will be described later, and when the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film of the resin composition are insufficient. Tend to be. The average particle size is more preferably 30 μm or less, further preferably 10 μm or less, particularly preferably 1 μm or less, and the maximum particle size is more preferably 80 μm or less, still more preferably 60 μm or less, particularly preferably 40 μm or less.
〔樹脂組成物〕
本発明の樹脂組成物は、(A)成分である樹脂を有機溶剤に溶解して樹脂溶液とし、(C)成分である「ハイドロタルサイトを含む無機微粒子及び/又は有機微粒子」を分散させ、さらに(B)成分であるエポキシ樹脂を添加混合して製造することができる。(Resin composition)
In the resin composition of the present invention, the resin as component (A) is dissolved in an organic solvent to obtain a resin solution, and the component (C) “inorganic fine particles and / or organic fine particles containing hydrotalcite” are dispersed, Furthermore, the epoxy resin which is (B) component can be added and mixed and manufactured.
本発明の樹脂組成物において、(C)成分として用いる「ハイドロタルサイトを含む無機微粒子及び/又は有機微粒子」の含有量は、前述したように、(A)成分100重量部に対して1〜250重量部とすることが好ましく、30〜200重量部とすることがより好ましく、50〜100重量部とすることが特に好ましい。(C)成分の含有量がこれよりも少ない場合、樹脂組成物ペーストの粘度及びチキソトロピー係数が低くなり、該ペーストの糸引きが増加するとともに印刷後の該ペーストの流れ出しが大きくなり、樹脂組成物の膜厚も薄膜化する傾向があり、電気特性が劣る傾向になる。また、(C)成分の含有量がこれより多い場合、樹脂組成物ペーストの粘度及びチキソトロピー係数が高くなり、該ペーストの基材への転写性が低下するとともに印刷膜中のボイド及びピンホールが増加する傾向がある。 In the resin composition of the present invention, the content of “inorganic fine particles and / or organic fine particles containing hydrotalcite” used as component (C) is 1 to 100 parts by weight of component (A) as described above. The amount is preferably 250 parts by weight, more preferably 30 to 200 parts by weight, and particularly preferably 50 to 100 parts by weight. When the content of the component (C) is less than this, the viscosity and thixotropy coefficient of the resin composition paste are decreased, the stringing of the paste is increased, and the flow of the paste after printing is increased, whereby the resin composition There is also a tendency for the film thickness to be reduced, and the electrical characteristics tend to be poor. Further, when the content of the component (C) is larger than this, the viscosity and thixotropy coefficient of the resin composition paste are increased, the transferability of the paste to the substrate is lowered, and voids and pinholes in the printed film are formed. There is a tendency to increase.
(A)成分の樹脂を溶解する有機溶剤としては、前述のように、非含窒素系極性溶媒として、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテルなどのエーテル系溶媒;ジメチルスルホキシド、ジエチルスルホキシド、ジメチルスルホン、スルホランなどの含硫黄系溶媒;γ−ブチロラクトン、酢酸セロソルブなどのエステル系溶媒;シクロヘキサノン、メチルエチルケトンなどのケトン系溶媒;トルエン、キシレンなどの芳香族炭化水素系溶媒、等が挙げられ、これらは単独で又は2種類以上組み合わせて使用することができる。生成する樹脂により溶解性が異なるので、樹脂を溶解可能な溶剤を選択して使用する。 (A) As an organic solvent which melt | dissolves resin of a component, as above-mentioned, ether solvents, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether, as a non-nitrogen-containing polar solvent; Sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone and sulfolane; ester solvents such as γ-butyrolactone and cellosolve acetate; ketone solvents such as cyclohexanone and methyl ethyl ketone; aromatic hydrocarbon solvents such as toluene and xylene; These may be used alone or in combination of two or more. Since the solubility varies depending on the resin to be produced, a solvent capable of dissolving the resin is selected and used.
熱硬化性樹脂((A)成分)の溶液に(C)成分:ハイドロタルサイトを含む無機及び/又は有機の微粒子を分散させる方法としては、通常、塗料分野で行われているロール練り、ミキサー混合等が適用され、十分な分散が行われる方法であれば良い。 As a method of dispersing inorganic and / or organic fine particles containing component (C): hydrotalcite in a solution of a thermosetting resin (component (A)), a roll kneading or a mixer usually used in the paint field is used. Any method may be used as long as mixing or the like is applied and sufficient dispersion is performed.
本発明の樹脂組成物には、塗工時の作業性及び被膜形成前後の膜特性を向上させるため、消泡剤、レベリング剤等の界面活性剤類、染料又は顔料等の着色剤類、熱安定剤、酸化防止剤、難燃剤、滑剤を添加することもできる。 In the resin composition of the present invention, surfactants such as antifoaming agents and leveling agents, colorants such as dyes and pigments, heat, Stabilizers, antioxidants, flame retardants, and lubricants can also be added.
本発明の樹脂組成物は、回転型粘度計での粘度が25℃で20Pa・s〜80Pa・sであり、特に30〜50Pa・sであることが好ましい。また、チキソトロピー係数が1.1以上であることが好ましい。粘度が20Pa・s未満であると、印刷後のペーストの流れ出しが大きくなるとともに膜厚が薄膜化する傾向があり、粘度が80Pa・sを超えると、ペーストの基材への転写性が低下するとともに印刷膜中のボイド及びピンホールが増加する傾向がある。またチキソトロピー係数が1.1未満であると、ペーストの糸引きが増加するとともに印刷後のペーストの流れ出しが大きくなり、膜厚も薄膜化する傾向がある。 The resin composition of the present invention has a viscosity at 25 ° C. of 20 Pa · s to 80 Pa · s, particularly preferably 30 to 50 Pa · s, at 25 ° C. Moreover, it is preferable that a thixotropy coefficient is 1.1 or more. If the viscosity is less than 20 Pa · s, the flow of paste after printing tends to increase and the film thickness tends to be reduced. If the viscosity exceeds 80 Pa · s, the transferability of the paste to the substrate decreases. At the same time, voids and pinholes in the printed film tend to increase. When the thixotropy coefficient is less than 1.1, the stringing of the paste increases, the flow of the paste after printing increases, and the film thickness also tends to be reduced.
ここで、樹脂組成物の粘度は、E型粘度計(東機産業社製、RE80U型)を用いて、試料量0.2mL又は0.5mLで測定した回転数10rpmの粘度として表される。またペーストのチキソトロピ−係数(TI値)はE型粘度計(東機産業社製、RE80U型)を用いて、試料量0.2mL又は0.5mLで測定した回転数1rpmと10rpmのペーストのみかけ粘度、η1とη10の比η1/η10として表される。 Here, the viscosity of the resin composition is expressed as a viscosity at a rotation speed of 10 rpm measured with a sample amount of 0.2 mL or 0.5 mL using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80U type). Also, the thixotropy coefficient (TI value) of the paste was applied only to pastes with rotation speeds of 1 rpm and 10 rpm measured with a sample volume of 0.2 mL or 0.5 mL using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model RE80U). Viscosity is expressed as the ratio η1 / η10 of η1 and η10.
本発明は、また上記の樹脂組成物を、フレキシブル配線板の配線パターンにスクリーン印刷した後、熱硬化させて硬化膜を形成し、保護膜としたフレキシブル配線板に好適に使用できる。特に、配線パターン部がスズメッキ処理されたフレキシブル配線板の表面の保護膜用途に適している。熱硬化の条件は、スズメッキ層の拡散を防ぎ、かつ保護膜として好適な低反り性、柔軟性を得る観点から、好ましくは、80℃〜130℃、特に好ましくは90℃〜120℃であるが、この範囲には限定されず、例えば、50〜200℃、中でも、50〜140℃の範囲で硬化させることもできる。また、加熱時間は、メッキ層の拡散を防ぎ、かつ保護膜として好適な低反り性、柔軟性を得る観点から、60〜150分、好ましくは、80〜120分であるが、この範囲には限定されず、1〜1,000分、例えば、5〜300分、中でも、10〜150分の範囲で硬化させることもできる。 The present invention can also be suitably used for a flexible wiring board in which the above resin composition is screen-printed on a wiring pattern of a flexible wiring board and then thermally cured to form a cured film to form a protective film. In particular, it is suitable for use as a protective film on the surface of a flexible wiring board in which the wiring pattern portion is tin-plated. The conditions for thermosetting are preferably 80 ° C. to 130 ° C., particularly preferably 90 ° C. to 120 ° C., from the viewpoint of preventing diffusion of the tin plating layer and obtaining low warpage and flexibility suitable as a protective film. It is not limited to this range, For example, it can also be made to harden | cure in the range of 50-200 degreeC, especially 50-140 degreeC. The heating time is 60 to 150 minutes, preferably 80 to 120 minutes from the viewpoint of preventing the diffusion of the plating layer and obtaining low warpage and flexibility suitable as a protective film. It is not limited, It can also be hardened in the range of 1 to 1,000 minutes, for example, 5 to 300 minutes, especially 10 to 150 minutes.
〔被膜形成材料〕
本発明の被膜形成材料は、上述した樹脂組成物を含み、各種電気製品や電子部品の被膜形成材料としてスクリーン印刷、ディスペンサ、スピンコートなどの塗布方法に好適に用いられる。特に、スクリーン印刷に好適に用いられる。[Coating material]
The film-forming material of the present invention contains the above-described resin composition and is suitably used as a film-forming material for various electrical products and electronic parts in coating methods such as screen printing, dispenser, and spin coating. In particular, it is suitably used for screen printing.
本発明による被膜形成材料は、例えば、半導体素子、プリント基板分野などの電子部品用オーバーコート材、液状封止材、層間絶縁膜、表面保護膜、ソルダレジスト層、接着層などとして好適に用いられる。また、エナメル線用ワニス、電気絶縁用含浸ワニス、注型ワニス、マイカ、ガラスクロス等の基材と組み合わせたシート用ワニス、MCL積層板用ワニス、摩擦材料用ワニスなどにも使用できる。また、樹脂被膜が回路基板等から剥離することなく、基材と樹脂同士の密着性及び印刷作業性に優れるため、信頼性の高い電子部品が得られる。 The film-forming material according to the present invention is suitably used, for example, as an overcoat material for electronic parts such as semiconductor elements and printed circuit boards, a liquid sealing material, an interlayer insulating film, a surface protective film, a solder resist layer, and an adhesive layer. . It can also be used for sheet varnishes, varnishes for MCL laminates, varnishes for friction materials, etc. in combination with a base material such as enameled wire varnish, impregnating varnish for electrical insulation, cast varnish, mica, glass cloth. In addition, since the resin coating is not peeled off from the circuit board or the like, the adhesion between the base material and the resin and the printing workability are excellent, so that a highly reliable electronic component can be obtained.
以下、本発明を実施例により詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
(合成例1:高分子樹脂の合成)
攪拌機、油分分離機付冷却管、窒素導入管及び温度計を備えた3リットルの四つ口フラスコに、γ-ブチロラクトン61.72g、1,6−ヘキサンジオール系ポリカーボネートジオール(ダイセル化学工業株式会社製、商品名「プラクセルCD−220」)74.64g(0.37モル)、4,4’−ジフェニルメタンジイソシアネート125.14g(0.46モル)トルエンジイソシアネート58.4g(0.34モル)を仕込み、150℃まで昇温し、150℃で4時間反応させた。(Synthesis Example 1: Synthesis of polymer resin)
In a 3 liter four-necked flask equipped with a stirrer, a condenser with an oil separator, a nitrogen inlet tube and a thermometer, 61.72 g of γ-butyrolactone, 1,6-hexanediol-based polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd.) , 74.64 g (0.37 mol) of trade name “Placcel CD-220”, 125.14 g (0.46 mol) of 4,4′-diphenylmethane diisocyanate, 58.4 g (0.34 mol) of toluene diisocyanate, The temperature was raised to 150 ° C. and reacted at 150 ° C. for 4 hours.
次いで、上記反応物に、無水トリメリット酸88.4g(0.46モル)を仕込み70℃で3時間反応させた。次いで再び4,4’−ジフェニルメタンジイソシアネート6.76g(0.027モル)、トルエンジイソシアネート0.0034g(0.00002モル)を仕込み、120℃で1時間、180℃で3時間反応させた。反応後、ブチルカルビトールアセテートを341.6g仕込み冷却し、さらに無水ピロメリット酸0.02g(0.0001モル)を仕込み、120℃で3時間反応させて、数平均分子量38,000の樹脂(ポリカーボネート変性ポリアミドイミド樹脂:本発明の(A)成分)を得た。数平均分子量は、反応時間毎に反応溶液を少量採取し、ガードナー製の気泡粘度計による粘度変化率を観察することで調整することができる。得られた樹脂をブチルカルビトールアセテートで希釈し、不揮発分50重量%のポリカーボネート変性ポリアミドイミド樹脂溶液を得た。 Next, 88.4 g (0.46 mol) of trimellitic anhydride was added to the reaction product and reacted at 70 ° C. for 3 hours. Subsequently, 6.76 g (0.027 mol) of 4,4′-diphenylmethane diisocyanate and 0.0034 g (0.00002 mol) of toluene diisocyanate were charged again and reacted at 120 ° C. for 1 hour and at 180 ° C. for 3 hours. After the reaction, 341.6 g of butyl carbitol acetate was charged and cooled, and 0.02 g (0.0001 mol) of pyromellitic anhydride was further charged and reacted at 120 ° C. for 3 hours to give a resin having a number average molecular weight of 38,000 ( Polycarbonate-modified polyamideimide resin (component (A) of the present invention) was obtained. The number average molecular weight can be adjusted by collecting a small amount of the reaction solution for each reaction time and observing the rate of change in viscosity using a Gardner bubble viscometer. The obtained resin was diluted with butyl carbitol acetate to obtain a polycarbonate-modified polyamideimide resin solution having a nonvolatile content of 50% by weight.
(実施例1)
上記(合成例1)で得られた数平均分子量が38,000のポリカーボネート変性ポリアミドイミド樹脂溶液に、該樹脂溶液の樹脂分100重量部に対して、溶剤処理液を1重量部、消泡剤(ビックケミー社製、商品名「BYK−051」)0.3重量部、レベリング剤(ビックケミー社製、商品名「BYK−354」)0.75重量部を配合し、20℃で10分間攪拌した。更に、硫酸バリウム(堺化学工業株式会社製、商品名「B−31」)を66.5重量部、タルク(日本タルク株式会社製、商品名「ST−2000」)を13.5重量部及びハイドロタルサイト(堺化学株式会社製、商品名「HT−P」)10重量部を予めビーズミルで分散したもの(本発明の(C)成分)を配合し、必要に応じてγ−ブチロラクトン等の溶剤を加えて50℃で1時間攪拌し、更に、本発明の(B)成分としてアミン型エポキシ樹脂(東都化成株式会社製、商品名「YH−434L」)を10重量部加え、20℃で1時間攪拌し、ポリカーボネート変性ポリアミドイミド樹脂組成物を得た。Example 1
In the polycarbonate-modified polyamideimide resin solution having a number average molecular weight of 38,000 obtained in the above (Synthesis Example 1), 1 part by weight of a solvent treatment solution and 100 parts by weight of an antifoaming agent with respect to 100 parts by weight of the resin content of the resin solution (BIC Chemie, trade name “BYK-051”) 0.3 parts by weight, leveling agent (Bick Chemie, trade name “BYK-354”) 0.75 parts by weight were blended and stirred at 20 ° C. for 10 minutes. . Furthermore, 66.5 parts by weight of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name “B-31”), 13.5 parts by weight of talc (manufactured by Nippon Talc Co., Ltd., trade name “ST-2000”) and Hydrotalcite (manufactured by Sakai Chemical Industry Co., Ltd., trade name “HT-P”) 10 parts by weight previously dispersed in a bead mill (component (C) of the present invention) is blended, and γ-butyrolactone or the like is added as necessary. A solvent was added and the mixture was stirred at 50 ° C. for 1 hour. Further, 10 parts by weight of an amine type epoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name “YH-434L”) was added as a component (B) of the present invention, and the mixture was heated at 20 ° C. The mixture was stirred for 1 hour to obtain a polycarbonate-modified polyamideimide resin composition.
(実施例2)
実施例1においてハイドロタルサイトを20重量部にした以外は、実施例1と全く同様の操作を行って、ポリカーボネート変性ポリアミドイミド樹脂組成物を得た。(Example 2)
Except that hydrotalcite was changed to 20 parts by weight in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.
(実施例3)
実施例1においてハイドロタルサイトを30重量部にした以外は、実施例1と全く同様の操作を行って、ポリカーボネート変性ポリアミドイミド樹脂組成物を得た。(Example 3)
Except that hydrotalcite was changed to 30 parts by weight in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.
(実施例4)
実施例1においてハイドロタルサイトを50重量部にした以外は、実施例1全く同様の操作を行って、ポリカーボネート変性ポリアミドイミド樹脂組成物を得た。Example 4
Except that hydrotalcite was changed to 50 parts by weight in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.
(比較例1)
合成例1において配合する樹脂を末端イソシアネートを無水ピロメリット酸で反応させたものではなく、オキシムで反応させたもの(酸無水物基及び/又はカルボキシル基を有しない樹脂)を用いた以外は、実施例1全く同様の操作を行って、ポリカーボネート変性ポリアミドイミド樹脂組成物を得た。(Comparative Example 1)
The resin blended in Synthesis Example 1 was not the one obtained by reacting the terminal isocyanate with pyromellitic anhydride, but the one reacted with oxime (resin having no acid anhydride group and / or carboxyl group), Example 1 Exactly the same operation was performed to obtain a polycarbonate-modified polyamideimide resin composition.
(比較例2)
実施例1においてハイドロタルサイトを配合しない以外は、実施例1全く同様の操作を行って、ポリカーボネート変性ポリアミドイミド樹脂組成物を得た。(Comparative Example 2)
Except that hydrotalcite was not blended in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.
上記の実施例及び比較例で得られた各ポリカーボネート変性ポリアミドイミド樹脂組成物及びこれらポリアミドイミド樹脂組成物の硬化被膜のポリイミドフィルムに対する貼り付き特性、印刷外観、および黒膨れの低減性を下記の方法で測定し、結果を(表1)に示した。 Each polycarbonate-modified polyamideimide resin composition obtained in the above Examples and Comparative Examples, and adhesion characteristics, printed appearance, and black blistering reduction properties of the cured film of these polyamideimide resin compositions to the polyimide film are described below. The results are shown in Table 1.
(保存安定性)
作製したポリカーボネート変性ポリアミドイミド樹脂組成物を回転型粘度計で粘度を測定し、48時間後に同様に粘度を測定し、作製時からの増粘率を算出した。数値が小さいもの程、保存安定性に優れる。(Storage stability)
The viscosity of the produced polycarbonate-modified polyamideimide resin composition was measured with a rotary viscometer, and the viscosity was measured in the same manner 48 hours later, and the rate of increase in viscosity from the time of production was calculated. The smaller the value, the better the storage stability.
(印刷外観)
35μmの銅箔上に、得られたポリカーボネート変性ポリアミドイミド樹脂組成物を印刷機(ニューロング株式会社製、商品名「LS―34GX」)とメッシュ版(株式会社ムラカミ製、150メッシュ)により、印刷速度100mm/secで30mm角を印刷し、印刷後の外観(泡跡、凝集物など)を100倍率の光学顕微鏡で観察した。
泡跡、凝集物などの欠陥が全く観察されなかったものを○、印刷部の一部に泡跡、凝集物などの欠陥が観察されるものを△、印刷部の全面に泡跡、凝集物などの欠陥が観察されたものを×として、評価した。(Print appearance)
The obtained polycarbonate-modified polyamideimide resin composition is printed on a 35 μm copper foil using a printing machine (trade name “LS-34GX” manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh manufactured by Murakami Co., Ltd.). A 30 mm square was printed at a speed of 100 mm / sec, and the appearance after the printing (foam marks, aggregates, etc.) was observed with an optical microscope of 100 magnification.
○ where no defects such as bubble marks and aggregates were observed, △ where defects such as bubble marks and aggregates were observed in a part of the printed part, and bubbles marks and aggregates over the entire printed part The case where defects such as were observed was evaluated as x.
(通電後の電極の黒膨れの有無)
ポリイミド基材上にライン幅15μm、スペース幅15μmで、くし型状にスズメッキされた銅電極を覆うように、得られたポリカーボネート変性ポリアミドイミド樹脂組成物を、印刷機(ニューロング株式会社製 商品名:LS−34GX)とメッシュ版(株式会社ムラカミ製 150メッシュ)を用いて、印刷速度100mm/secで印刷し、空気雰囲気下で120℃、60分加熱硬化してポリカーボネート変性ポリアミドイミド樹脂の硬化被膜付きポリイミド基材くし型電極を得た。得られたポリカーボネート変性ポリアミドイミド樹脂硬化被膜付きポリイミド基材くし型電極を、連続抵抗測定機(IMV株式会社製、商品名「Ion Migration Tester MIG−8600」)と不飽和型プレッシャークッカ(株式会社平山製作所製、商品名「HAST PC−422R8D」)を用いて、温度120℃、湿度85%、印加電圧60V、印加時間100時間の条件で通電し、通電後の電極の黒膨れの有無を100倍率の光学顕微鏡で観察した。
黒膨れが無いものを○とし、僅かに黒膨れが発生するものを△とし、黒膨れが多量に観察されたものを×として、評価した。(Check for black swelling of the electrode after energization)
The resulting polycarbonate-modified polyamideimide resin composition was covered with a printing machine (manufactured by Neurong Co., Ltd.) so as to cover a copper electrode tin-plated in a comb shape with a line width of 15 μm and a space width of 15 μm. : LS-34GX) and a mesh plate (150 mesh manufactured by Murakami Co., Ltd.), printed at a printing speed of 100 mm / sec, and cured by heating in an air atmosphere at 120 ° C. for 60 minutes to form a cured coating of a polycarbonate-modified polyamideimide resin A polyimide substrate comb-type electrode was obtained. The resulting polyimide-based comb-shaped electrode with a polycarbonate-modified polyamideimide resin cured film was subjected to continuous resistance measurement (IMV Corporation, trade name “Ion Migration Tester MIG-8600”) and unsaturated pressure cooker (Hirayama Corporation). Using a product name “HAST PC-422R8D” manufactured by Seisakusho Co., Ltd.) and energizing under conditions of a temperature of 120 ° C., a humidity of 85%, an applied voltage of 60 V, and an applied time of 100 hours. Were observed with an optical microscope.
Evaluation was made with a circle having no black blisters as ◯, a sample with slight black blisters as Δ, and a sample with a large amount of black blisters as x.
(貼り付き性)
印刷後のポリカーボネート変性ポリアミドイミド樹脂組成物を空気環境下で120℃、60分で硬化させた試験片と、ポリイミドフィルムと、更に銅版とを重ね合わせ、2kgの分銅で荷重し、ポットプレートで90〜120℃、30秒加熱後の試験片とポリイミドフィルムとの貼り付き性を測定した。貼り付きが生じ始めた温度により評価した。
貼り付きが生じ始めた温度が高い方が好ましい。(Adhesiveness)
A test piece obtained by curing the polycarbonate-modified polyamideimide resin composition after printing in an air environment at 120 ° C. for 60 minutes, a polyimide film, and a copper plate are overlaid, loaded with a weight of 2 kg, and 90 μm in a pot plate. The sticking property between the test piece and the polyimide film after heating at ˜120 ° C. for 30 seconds was measured. Evaluation was based on the temperature at which sticking began to occur.
It is preferable that the temperature at which sticking begins to occur is higher.
以上の結果から、次のことが確認できる。
すなわち、比較例1と他の例との比較から、末端イソシアネートを無水ピロメリット酸で修飾した場合、アミン型エポキシ樹脂との反応が促進され、硬化後のポリイミドフィルムとの貼り付きが軽減されることが分かる。
また、実施例2〜4及び比較例2では、ハイドロタルサイトの配合量を増やすことで増粘を軽減できる。さらに、ハイドロタルサイトを配合することにより通電後の電極の黒膨れを軽減することができる。しかし、過剰な配合量は印刷外観上不具合を生じた。From the above results, the following can be confirmed.
That is, from the comparison between Comparative Example 1 and other examples, when the terminal isocyanate is modified with pyromellitic anhydride, the reaction with the amine type epoxy resin is promoted, and the sticking with the cured polyimide film is reduced. I understand that.
Moreover, in Examples 2-4 and Comparative Example 2, thickening can be reduced by increasing the blending amount of hydrotalcite. Furthermore, the black swelling of the electrode after electricity supply can be reduced by mix | blending a hydrotalcite. However, an excessive blending amount caused a problem in printing appearance.
以上説明したように、本発明にかかる樹脂組成物及び被膜形成材料は、各種電気製品や電子部品の被膜形成材料として、スクリーン印刷、ディスペンサ、スピンコートなどの塗布方法に好適に用いられる。また、硬化後のポリイミドフィルムとの貼り付きが生じにくいことから、ポリイミドフィルムと硬化膜間のスペーサを排除できるなど作業性、コスト面で有用である。 As described above, the resin composition and the film-forming material according to the present invention are suitably used for coating methods such as screen printing, dispenser, and spin coating as film-forming materials for various electric products and electronic parts. Moreover, since it is hard to stick with the polyimide film after hardening, it is useful in terms of workability and cost, such as eliminating the spacer between the polyimide film and the cured film.
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JP2003138015A (en) * | 2001-11-07 | 2003-05-14 | Hitachi Chem Co Ltd | Polyamideimide resin paste and coating material comprising the same |
JP2003198105A (en) * | 2001-12-28 | 2003-07-11 | Hitachi Chem Co Ltd | Resin paste and flexible wiring board using the same |
JP2003213083A (en) * | 2002-01-24 | 2003-07-30 | Nippon Kayaku Co Ltd | Epoxy resin composition and flexible printed wiring board material using the same |
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