JP4378577B2 - Heat resistant resin composition, adhesive film using the same, and polyimide film with adhesive layer - Google Patents
Heat resistant resin composition, adhesive film using the same, and polyimide film with adhesive layer Download PDFInfo
- Publication number
- JP4378577B2 JP4378577B2 JP16032099A JP16032099A JP4378577B2 JP 4378577 B2 JP4378577 B2 JP 4378577B2 JP 16032099 A JP16032099 A JP 16032099A JP 16032099 A JP16032099 A JP 16032099A JP 4378577 B2 JP4378577 B2 JP 4378577B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- siloxane
- resistant resin
- film
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims description 32
- 229920006015 heat resistant resin Polymers 0.000 title claims description 31
- 239000002313 adhesive film Substances 0.000 title claims description 21
- 229920001721 polyimide Polymers 0.000 title claims description 18
- 239000012790 adhesive layer Substances 0.000 title claims description 12
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- -1 siloxane diamine Chemical class 0.000 claims description 32
- 239000004962 Polyamide-imide Substances 0.000 claims description 18
- 239000003822 epoxy resin Substances 0.000 claims description 18
- 229920002312 polyamide-imide Polymers 0.000 claims description 18
- 229920000647 polyepoxide Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 description 22
- 239000004065 semiconductor Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 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 8
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000002798 polar solvent Substances 0.000 description 7
- 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 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 6
- 229910000071 diazene Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(N*)OCI Chemical compound CC(C)(N*)OCI 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- PJCCVNKHRXIAHZ-UHFFFAOYSA-N 4-[4-[[4-(4-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1CC(C=C1)=CC=C1OC1=CC=C(N)C=C1 PJCCVNKHRXIAHZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KTPIWUHKYIJBCR-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-4-ene-1,2-dicarboxylate Chemical compound C1C=CCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KTPIWUHKYIJBCR-UHFFFAOYSA-N 0.000 description 1
- LSDYQEILXDCDTR-UHFFFAOYSA-N bis[4-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 LSDYQEILXDCDTR-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 210000001217 buttock Anatomy 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- HGTDVVTWYKXXMI-UHFFFAOYSA-N pyrrole-2,5-dione;triazine Chemical compound C1=CN=NN=C1.O=C1NC(=O)C=C1 HGTDVVTWYKXXMI-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- PYGKDFLMCGZPHX-UHFFFAOYSA-N tris(oxiran-2-ylmethyl) phosphate Chemical compound C1OC1COP(OCC1OC1)(=O)OCC1CO1 PYGKDFLMCGZPHX-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、耐熱性樹脂組成物、これを用いた接着フィルム及び接着層付ポリイミドフィルムに関する。
【０００２】
【従来の技術】
近年、各種電子機器の小型化、軽量化が急速に進むのに伴い、電子部品の搭載密度も高くなり、それに用いられる配線板、半導体パッケージ等に要求される特性も多様化してきている。このような中でプリント配線板は、配線占有面積の小型、高密度になり多層配線板（ビルドアップ配線板）化、フレキシブル配線板 （ＦＰＣ）化、フレキシブルリジッド配線板（ＦＲＣ）化等の要求が益々高まってきている。これらの配線板は、製造工程において種々の接着剤又は接着フィルムを用いているが、接着性及び耐熱性に優れ、かつ環境にやさしい非ハロゲン系で十分な難燃性を有している接着剤又は接着フィルムはなかった。
【０００３】
また、半導体パッケージにおいても小型化、軽量化及び高密度化が急速に進み、その開発はめざましいが、その中の材料としては各種ポリイミドフィルムが広く用いられている。このポリイミドフィルムに対する接着性に優れ、耐熱性が良く、かつ環境にやさしい非ハロゲン系で十分な難燃性を有している接着剤及び封止材はなかった。
【０００４】
これまでの耐熱性樹脂組成物は、ハロゲン系化合物及びアンチモン系化合物を併用配合することでいわゆる「フリーラジカルトラップ効果」やオキシハロゲン化アンチモンの脱水炭化作用を利用するものが広く知られているが、燃焼時にダイオキシン等の有毒物質が出る環境汚染の問題が解決していない。
【０００５】
【発明が解決しようとする課題】
請求項１記載の発明は、接着性及び耐熱性に優れ、各種プリント配線板、半導体パッケージ用接着剤、接着フィルム、半導体パッケージ用封止材に好適である耐熱性樹脂組成物を提供する。請求項２記載の発明は、請求項１記載の発明の効果に加えて、さらに非ハロゲン系で十分な難燃性、接着性及び耐熱性に優れ、各種プリント配線板、半導体パッケージ用接着剤、接着フィルム、半導体パッケージ用封止材に好適である耐熱性樹脂組成物を提供する。
【０００６】
請求項３記載の発明は、非ハロゲン系で十分な難燃性、接着性及び耐熱性に優れ、各種プリント配線板、半導体パッケージ用に有用である接着フィルムを提供する。請求項４記載の発明は、非ハロゲン系で十分な難燃性、接着性及び耐熱性に優れ、各種プリント配線板、半導体パッケージ用に有用である接着層付ポリイミドフィルムを提供する。
【０００７】
【課題を解決するための手段】
本発明は、（Ａ）シロキサン変性ポリアミドイミド樹脂、（Ｂ）エポキシ化ポリブタジエン及び（Ｃ）エポキシ樹脂を含有してなる耐熱性樹脂組成物に関する。
【０００８】
また、本発明は、（Ａ）シロキサン変性ポリアミドイミド樹脂が、芳香族環を３個以上有するジアミン及びシロキサンジアミンの混合物と無水トリメリット酸とを反応させて得られる下記一般式（Ｉ）及び下記一般式（II）で表されるジイミドジカルボン酸を含む混合物と下記一般式（III）で表される芳香族ジイソシアネートとを反応させて得られるシロキサン変性ポリアミドイミド樹脂である前記耐熱性樹脂組成物に関する。
【０００９】
【化８】
【化９】
【００１０】
【化１１】
【化１２】
【００１１】
【化１４】
【００１２】
また、本発明は、さらに（Ｄ）リン系化合物又は（Ｅ）無機充填剤を含有してなる前記耐熱性樹脂組成物に関する。
【００１３】
また、本発明は、前記耐熱性樹脂組成物からなる接着フィルムに関する。
また、ポリイミドフィルム上に接着層として、前記接着フィルムが積層された接着層付ポリイミドフィルムに関する。
【００１４】
【発明の実施の形態】
以下、本発明について詳細に説明する。なお、本発明における（メタ）アクリル酸とは、アクリル酸及びそれに対応するメタクリル酸を意味し、（メタ）アクリレートとは、アクリレート及びそれに対応するメタクリレートを意味する。
【００１５】
本発明の耐熱性樹脂組成物は、（Ａ）シロキサン変性ポリアミドイミド樹脂、（Ｂ）ゴム系エラストマー及び（Ｃ）熱硬化性樹脂を含有してなる。
【００１６】
上記（Ａ）シロキサン変性ポリアミドイミド樹脂は、芳香族環を３個以上有するジアミン及びシロキサンジアミンの混合物と無水トリメリット酸とを反応させて得られる前記一般式（Ｉ）及び前記一般式（II）で表されるジイミドジカルボン酸を含む混合物と前記一般式（III）で表される芳香族ジイソシアネートとを反応させて得られるシロキサン変性ポリアミドイミド樹脂であることが好ましい。
【００１７】
上記一般式（II）中、炭素数１〜２０のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、これらの構造異性体等が挙げられる。
上記一般式（II）中、炭素数６〜１８のアリール基としては、例えば、フェニル基、トリル基、キシリル基、ビフェニル基、ナフチル基、アントリル基、フェナントリル基等が挙げられ、ハロゲン原子、アミノ基、ニトロ基、シアノ基、メルカプト基、アリル基、炭素数１〜２０のアルキル基等で置換されていてもよい。
【００１８】
前記芳香族環を３個以上有するジアミンとしては、例えば、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン（以下、ＢＡＰＰと略す）、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、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−（４−アミノフェノキシ）フェニル］メタン、４，４′−ビス（４−アミノフェノキシ）ビフェニル、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、ビス［４−（４−アミノフェノキシ）フェニル］ケトン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン等が挙げられ、シロキサン変性ポリアミドイミド樹脂の特性のバランスとコストの見地からは、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン （ＢＡＰＰ）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される。
【００１９】
本発明で用いるシロキサンジアミンとしては、公知のものが使用できるが、例えば、下記一般式（IV）で表されるものであることが好ましい。
【化１５】
【００２０】
上記一般式（IV）中、２価の有機基としては、例えば、メチレン基、エチレン基、プロピレン基等のアルキレン基、フェニレン基、トリレン基、キシリレン基等のアリーレン基などが挙げられる。
【００２１】
このようなシロキサンジアミンとしては下記式に示すもの等が挙げられる。
【００２２】
商業的に入手可能なものとしては、例えば、これらの中でもシロキサン系両末端アミンであるアミノ変性シリコーンオイルＸ−２２−１６１ＡＳ（アミン当量４５０、信越化学工業(株)製商品名）、Ｘ−２２−１６１Ａ（アミン当量８４０、信越化学工業(株)製商品名）、Ｘ−２２−１６１Ｂ（アミン当量１５００、信越化学工業(株)製商品名）、ＢＹ１６−８５３（アミン当量６５０、東レダウコーニングシリコーン(株)製商品名）、ＢＹ１６−８５３Ｂ（アミン当量２２００、東レダウコーニングシリコーン(株)製商品名）等が挙げられる。
【００２３】
前記一般式（III）で示される芳香族ジイソシアネートとしては、例えば、４ ，４′−ジフェニルメタンジイソシアネート（以下、ＭＤＩと略す）、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ナフタレン−１，５−ジイソシアネート、２，４−トリレンダイマー等が挙げられ、可とう性付与及び結晶性防止の見地から４，４′−ジフェニルメタンジイソシアネート （ＭＤＩ）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される。
また、耐熱性の見地から、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シシアネート、イソホロンジイソシアネート等の脂肪族ジイソシアネートを上記芳香族ジイソシアネートに対して、５〜１０モル％程度で併用することができる。
【００２４】
また、耐熱性の見地から前記ジイミドカルボン酸に加えて、テレフタル酸、フタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸、アジピン酸、セバシン酸、デカン二酸、ドデカン二酸、ダイマー酸等の脂肪族ジカルボン酸などを上記ジイミドカルボン酸に対して５〜１０モル％程度で併用することができる。
【００２５】
本発明で用いる（Ａ）成分のシロキサン変性ポリアミドイミド樹脂は、例えば、芳香族環を３個以上有するジアミン（１）及びシロキサンジアミン（２）の混合物（(１)／(２)＝０．１／９９．９〜９９．９／０．１モル比）と無水トリメリット酸（以下、ＴＭＡと略す）を（(１)＋(２)）の合計モル数とＴＭＡのモル比が１／２．２０〜１／２．０５で非プロトン性極性溶媒の存在下に、５０〜９０℃程度で０．２〜１．５時間程度反応させ、さらに水と共沸可能な芳香族炭化水素を非プロトン性極性溶媒の０．１〜０．５重量％程度で投入し、１２０〜１８０℃で反応を行い、前記一般式（Ｉ）で表される芳香族ジイミドジカルボン酸及び前記一般式（II）で表されるシロキサンジイミドジカルボン酸を含む混合物を製造し、これと前記一般式（III）で表される芳香族ジイソシアネート（３）とを１５０〜２５０℃程度で０．５〜３時間程度反応〔((１)＋(２))／(３)＝１／１．５０〜１／１．０５モル比〕を行うことで製造できる。
【００２６】
また、芳香族ジイミドジカルボン酸を製造した後、その溶液を１５０〜２５０℃程度にすることでその溶液から芳香族炭化水素を除去し、これと芳香族ジイソシアネートとの反応を行うことによって製造することもできる。
また、シロキサン変性ポリアミドイミド樹脂は非プロトン性極性溶媒を含むワニスであることが好ましい。
【００２７】
上記芳香族環を３個以上有するジアミン（１）及びシロキサンジアミン（２）の混合物の混合比としては、(１)／(２)＝０．１／９９．９〜９９．９／０．１モル比であることが好ましく、０．１／９９．９〜７０．０／３０．０モル比であることがより好ましい。このモル比が０．１／９９．９未満では得られる樹脂の分子量が低下する傾向があり、９９．９／１を超えると得られる樹脂の樹脂骨格が剛直になる傾向がある。
【００２８】
さらに上記混合物と無水トリメリット酸（ＴＭＡ）とを反応させ、前記一般式（Ｉ）及び前記一般式（II）で表されるジイミドジカルボン酸を含む混合物を得るためのモル比は（(１)＋(２)）／ＴＭＡ＝１／２．２０〜１／２．０５であることが好ましく、１／２．１５〜１／２．１０であることがより好ましい。このモル比が１／２．２０未満ではＴＭＡが残存し、最終的に得られる樹脂の分子量が低下する傾向があり、１／２．０５を超えるとジアミンが残存し、最終的に得られる樹脂の分子量が低下する傾向がある。
【００２９】
次いで前記一般式（Ｉ）及び前記一般式（II）で表されるジイミドジカルボン酸の混合物と前記一般式（III）で表される芳香族ジイソシアネート（３）とを反応させ、シロキサン変性ポリアミドイミド樹脂を得るためのモル比は、（(１)＋(２)）／（３）＝１／１．５０〜１／１．０５であることが好ましく、１／１．４〜１／１．１であることがより好ましい。このモル比が１／１．５０未満では得られる樹脂の分子量が低下する傾向があり、１／１．０５を超えると得られる樹脂の分子量が低下する傾向がある。
【００３０】
前記非プロトン性極性溶媒としては、芳香族環を３個以上有するジアミン、シロキサンジアミン及びＴＭＡと反応しない有機溶媒であることが好ましく、例えば、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン、スルホラン、シクロヘキサノン等が挙げられる。イミド化反応には、高温を要するため沸点の高いＮ−メチル−２−ピロリドンがより好ましい。これらは単独で又は２種類以上を組み合わせて使用される。
【００３１】
これらの非プロトン性極性溶媒中に含まれる水分量は０．１〜０．２重量％とすることが好ましい。この水分量が０．２重量％を超えるとＴＭＡが水和して生成するトリメリット酸により、十分に反応が進行せず、ポリマの分子量が低下する傾向がある。また、本発明で使用する非プロトン性極性溶媒の使用量は、芳香族環を３個以上有するジアミン、シロキサンジアミン、無水トリメット酸及び非プロトン性極性溶媒の総量に対して、１０〜７０重量％の範囲になることが好ましい。この使用量が１０％未満ではＴＭＡの溶解性が低下し、十分な反応が行えなくなる傾向があり、７０重量％を超えると工業的製造法として不利である傾向がある。
【００３２】
前記芳香族炭化水素としては、例えば、トルエン、キシレン等が挙げられる。
【００３３】
（Ａ）シロキサン変性ポリアミドイミド樹脂の重量平均分子量は、２０，０００〜３００，０００であることが好ましく、２５，０００〜２００，０００であることがより好ましく、３０，０００〜１５０，０００であることが特に好ましい。なお、本発明における重量平均分子量は、ゲルパーミエーションクロマトグラフィー法により測定され、標準ポリスチレンを用いて作成した検量線により換算されたものである。
【００３４】
本発明における（Ｂ）ゴム系エラストマーとしては、例えば、アクリロニトリルゴム、ポリブタジエンゴム、アクリル−ブタジエンゴム、シリコーンゴム等が挙げられる。これらは単独で又は２種類以上を組み合わせて使用される。上記アクリルゴムとしては、例えば、アクリロニトリルと他の（メタ）アクリル系モノマとの共重合体、これらのエポキシ変性物等が挙げられ、例えば、グリシジルアクリレートとの共重合物、東都化成社製のエポトートＹＲ５２８、ＹＲ５７０等が挙げられる。
【００３５】
上記ポリブタジエンゴムとしては、例えば、ブタジエンゴム、ブタジエン−イソプレンゴム、ブタジエン−スチレンゴム、これらのエポキシ変性物等が挙げられ、例えば、例えばダイセル化学工業(株)製のエポキシ化ポリブタジエン、エポリードＰＢ３６００、ＰＢ４７００、エポキシ化ブタジエン−スチレン等が挙げられる。接着性及び耐熱性の見地からは、エポキシ変性物であることが好ましく、エポリードＰＢ３６００であることがより好ましい。
【００３６】
アクリル−ブタジエンゴムとしては、例えば、アクリロニトリル−ブタジエン（ＮＢＲゴム）、アクリル−イソプレン、アクリル−ブタジエン−イソプレン、アクリル−ブタジエン−スチレン、これらのカルボン酸変性物、これらのエポキシ変性物等が挙げられ、例えば、Ｂ．Ｆ．グッドリッチ社製のハイカー、日本合成ゴム社製のＸＥＲ−８１、ＸＥＲ−９１、ＰＮＲ−１Ｈ、東都化成社製のエポトートＹＲ４５０、ＹＲ２０７等が挙げられる。
【００３７】
上記シリコーンゴムとしては、オルガノポリシロキサンを主成分としたものであることが好ましく、例えば、ポリジメチルシロキサン系、ポリメチルフェニルシロキサン系、ポリジフェニルシロキサン系、一部をビニル基、アルコキシ基等で変性したもの、エポキシ変性物等が挙げられ、例えば、ワッカー社製ＳＹ４３０、東レダウコーニングシリコーン社製ＳＨ６０４０等が挙げられる。
【００３８】
これら上記のエポキシ変性物の中でＰＢ３６００は特性的に接着性、耐熱性の点から特に好ましい。
【００３９】
本発明における（Ｃ）熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、ポリエステル樹脂、ビスマレイミドトリアジン樹脂等が挙げられる。接着性及び取り扱い性の見地からはエポキシ樹脂が好ましく、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂及びその変性物、ビキシレニルジグリシジルエーテル、ＹＤＣ１３１２（東都化成社製）、エポトートＹＤ−８１２５（東都化成社製）、ＴＭＨ５７４（住友化学工業(株)製）、エピコート１０３１Ｓ（油化シェルエポキシ(株)製）等の芳香族系エポキシ樹脂、ネオペンチルグリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、テトラヒドロフタル酸ジグリシジルエステル等の脂肪族系エポキシ樹脂、トリグリシジルイソシアネート等の複素環式エポキシ化合物などが挙げられる。
【００４０】
これらの中では２個以上のグリシジル基を有するエポキシ樹脂とその硬化促進剤を用いることが好ましい。またグリシジル基は多いほどより好ましく、３個以上であれば特に好ましい。グリシジル基の数により、配合量が異なり、グリシジル基が多い程、シロキサン変性ポリアミドイミド樹脂に対する配合量が少なくても良い。また、エポキシ樹脂の硬化剤を併用すればさらに好ましい。
【００４１】
上記硬化促進剤及び硬化剤としては、エポキシ樹脂と反応するもの又は硬化を促進させるものであれば特に制限はなく、例えば、アミン類、イミダゾール類、多官能フェノール類、酸無水物類等が挙げられる。
上記アミン類としては、例えば、ジシアンジアマイド、ジアミノジフェニルメタン、グアニル尿素等が挙げられる。
上記イミダゾール類としては、例えば、２−エチル−４−メチルイミダゾール等のアルキル基置換イミダゾール、ベンゾイミダゾールなどが挙げられる。
上記多官能フェノール類としては、例えば、ヒドロキノン、レゾルシノール、ビスフェノールＡ及びこれらのハロゲン化合物、前記多官能フェノール類とホルムアルデヒドとの付加縮合物であるノボラックフェノール型フェノール樹脂、レゾール型フェノール樹脂等が挙げられる。
上記酸無水物類としては、例えば、無水フタル酸、ベンゾフェノンテトラカルボン酸二水和物、メチルハイミック酸等が挙げられるが、反応性及びポットライフの見地からは、イミダゾール類又はアミン類を用いる事が特に好ましい。
これらは単独で又は２種類以上を組み合わせて使用される。
【００４２】
本発明において必要に応じて含有される（Ｄ）リン系化合物としては、例えば、トリフェニルホスフェ−ト、トリグリシジルホスフェ−ト、ポリホスフェ−ト化合物、レゾルシンポリホスフェ−ト化合物、トリキシレニルホスフェ−ト、芳香族縮合リン酸エステル及びビフェニル型リン酸エステル（大八化学工業(株)製商品名ＣＲ−７４７等）等のリン酸エステル類等の有機リン系化合物などが挙げられる。
【００４３】
本発明において必要に応じて含有される（Ｅ）無機充填剤としては、例えば、水酸化アルミニウム（昭和電工(株)製商品名ハイジライトＨ−４２ＳＴＥ等）、水酸化マグネシウム（協和化学工業(株)製商品名キスマ５ＰＨ）、アルミン酸カルシウム、シリコーンポリマー粉末等が挙げられるが、結晶水を含有する水酸化アルミニウム又は水酸化マグネシウムがより好ましい。これらは単独で又は２種類以上を組み合わせて使用される。
【００４４】
難燃性を一層向上させるためには、（Ｄ）成分のリン系化合物及び（Ｅ）成分の無機充填剤を併用することが好ましい。
【００４５】
本発明における（Ｂ）ゴム系エラストマーの配合量は、接着性、屈曲性、耐熱性の見地から、（Ａ）シロキサン変性ポリアミドイミド樹脂１００重量部に対して５〜２０重量部であることが好ましく、７〜１２重量部であることが特に好ましい。この配合量が５重量部未満では接着性が低下する傾向があり、２０重量部を超えるとはんだ耐熱性、接着性及びガラス転移温度が低下する傾向がある。
【００４６】
本発明における（Ｃ）熱硬化性樹脂の配合量は、接着性、屈曲性及び耐熱性の見地から、（Ａ）シロキサン変性ポリアミドイミド樹脂１００重量部に対して１０〜１５０重量部であることが好ましく、３０〜７０重量部であることが特に好ましい。この配合量が１０重量部未満では硬化物の架橋密度が低下し、絶縁性が劣る傾向があり、１５０重量部を超えると未反応の熱硬化性樹脂が残存し、硬化物のガラス転移温度が低下する傾向がある。
【００４７】
本発明において必要に応じて含有される硬化促進剤又は硬化剤の配合量は、アミン類の場合はアミンの活性水素の当量とエポキシ樹脂のエポキシ当量が、それぞれほぼ等しくなる量が好ましい。イミダゾール類の場合は、エポキシ樹脂１００重量部に対して、それぞれ０．１〜１０．０重量部であることが好ましい。多官能フェノール類の場合、エポキシ樹脂のエポキシ基１当量に対して、それぞれ０．６〜１．２水酸基当量であることが好ましい。この配合量は、上記配合量より少なければ未硬化のエポキシ樹脂が残存し、Ｔｇが低くなる傾向があり、上記配合量を超えると未反応の硬化促進剤及び硬化剤が残存し、絶縁性が低下する傾向がある。
【００４８】
本発明において必要に応じて含有される（Ｄ）リン系化合物の配合量は、（Ａ）＋（Ｂ）＋（Ｃ）成分の総量１００重量部に対して５〜２５重量部であることが好ましく、１０〜１５重量部であることがより好ましい。この配合量が５重量部未満では難燃性が不十分となる傾向があり、２５重量部を超えると接着性及びはんだ耐熱性が低下する傾向がある。
【００４９】
本発明において必要に応じて含有される（Ｅ）無機充填剤の配合量は、（Ａ）＋（Ｂ）＋（Ｃ）成分の総量１００重量部に対して５０〜８０重量部であることが好ましく、５０〜６０重量部であることがより好ましい。この配合量が５０重量部未満では難燃性が低下する傾向があり、８０重量部を超えると接着性、はんだ耐熱性が低下する傾向がある。
【００５０】
本発明では、これら組成物を有機溶媒中で混合して、固形分３０〜４０重量％程度の耐熱性樹脂組成物とすることが好ましい。
上記有機溶媒としては、溶解性が得られるものであれば特に制限はなく、例えば、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン、スルホラン、シクロヘキサノン等が挙げられる。
【００５１】
また、本発明の耐熱性樹脂組成物には上記各成分の他に必要に応じて、分散剤（Disperbyk１１０等）、カップリング剤、顔料、レベリング剤、消泡剤、イオントラップ剤などを適宜配合しても良い。
【００５２】
本発明の耐熱性樹脂組成物を用いて接着層を形成するには、例えば、そのまま塗布して接着層を形成してもよいし、接着フィルムの形態にして耐熱性樹脂組成物の層を積層することによって接着層を形成してもよい。また、接着フィルムを使用するときは積層してから下記支持基材を除去してもよいし、積層する前に除去してもよい。
【００５３】
本発明の接着フィルムは、例えば、支持基材上に、所定の有機溶剤に溶解した耐熱性樹脂組成物を塗布後、加熱又は熱風吹き付けにより溶剤を乾燥させて作製することができる。
上記支持基材としては、例えば、ポリエチレン、ポリ塩化ビニル等のポリオレフィン、ポリエチレンテレフタレート等のポリエステル、ポリカーボネート、テフロンフィルム、離型紙、銅箔、アルミニウム箔等の金属箔などが挙げられる。支持基材の厚みは１０〜１５０μｍが好ましい。なお、支持基材にはマッド処理、コロナ処理、離型処理等を施してもよい。
上記有機溶剤としては、特に制限はなく、例えば、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類、セロソルブ、ブチルセロソルブ等のセロソルブ類、カルビトール、ブチルカルビトール等のカルビトール類、トルエン、キシレン等の芳香族炭化水素、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドンなどが挙げられる。これらは単独で又は２種類以上を組み合わせて使用される。
【００５４】
上記支持基材上に積層された耐熱性樹脂組成物の厚みは５〜５０μｍであることが好ましく、１０〜４０μｍであることがより好ましい。
上記接着フィルムの形態としては、例えば、ある一定の長さで裁断されたシート状、ロール状等が挙げられる。保存性、生産性及び作業性の見地からは、耐熱性樹脂組成物と反対側の面に保護フィルムをさらに積層し、ロール状に巻きとって貯蔵することが好ましい。
上記保護フィルムとしては、例えば、支持基材と同じくポリエチレン、ポリ塩化ビニル、ポリプロピレン等のポリオレフィン、ポリエチレンテレフタレート等のポリエステル、離型紙などが挙げられる。上記保護フィルムの厚みは１０〜１００μｍであることが好ましい。なお、保護フィルムにはマッド処理、エンボス加工、離型処理を施してもよい。
【００５５】
本発明の接着フィルムは、例えば、ポリイミドフィルム等に積層することで接着層付ポリイミドフィルムとすることができ、さらに金属箔を積層することでフレキシブルプリント配線板用基板等とすることができる。
【００５６】
【実施例】
以下実施例により本発明を具体的に説明する。
【００５７】
（合成例１）
還流冷却器を連結したコック付き２５ミリリットルの水分定量受器、温度計、撹拌器を備えた１リットルのセパラブルフラスコに芳香族環を３個以上有するジアミンとしてＢＡＰＰ（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）、シロキサンジアミンとして反応性シリコーンオイルＸ−２２−１６１−ＡＳ（信越化学工業(株)製商品名、アミン当量４１６）、ＴＭＡ（無水トリメリット酸）、非プロトン性極性溶媒としてＮＭＰ（Ｎ−メチル−２−ピロリドン）をそれぞれ表１に示した配合比で仕込み、８０℃で３０分間撹拌した。そして、水と共沸可能な芳香族炭化水素としてトルエン１００ミリリットルを投入してから温度を上げ、１６０℃で２時間還流させた。
【００５８】
水分定量受器に水が約３．６ミリリットル以上溜まっていること、水の流出が見られなくなっていることを確認し、水分定量受器に溜まっている流出水を除去しながら、１９０℃まで温度を上げてトルエンを除去した。
その後、溶液を室温に戻し、芳香族ジイソシアネートとしてＭＤＩ（４，４′−ジフェニルメタンジイソシアネート）を表１に示した量を投入し、１９０℃で２時間反応させた。反応終了後、シロキサン変成ポリアミドイミド樹脂のＮＭＰ溶液Ａ−１を得た。
【００５９】
【表１】
（実施例１〜４）
合成例１で得られたシロキサン変性ポリアミドイミド樹脂Ａ−１に対して表２に示す材料を配合し、樹脂が均一になるまで１時間撹拌した後、さらに無機充填剤と樹脂が均一になるまで三本ロールで混練し、脱泡のため室温で２４時間静置して耐熱性樹脂組成物を得た。
【００６１】
【表２】
また、得られた耐熱性樹脂組成物を厚さ５０μｍのテフロンフィルム（日東電工(株)製商品名：ナフロンテープＴＯＭＢＯ９００１）に乾燥後の膜厚が２０μｍになるように塗布し、１３０℃で３分間乾燥させたものを作製して、乾燥機で１８０℃×１２０分間硬化させ、接着フィルムを得、上記接着フィルムを用いて厚さ２５μｍのポリイミドフィルム（東レ・デュポン(株)製商品名：カプトン１００Ｈ）表面上に上記耐熱性樹脂組成物の層を張り合わせ、テフロンフィルムを除去した。次いで、３５μｍの圧延銅箔（日鉱グールドホイール(株)製商品名：ＢＨＹ−２２Ｂ−Ｔ）の粗化面側を張り合わせ、温度１２０℃、圧力５kgf/cm2で熱ロールラミネートを行って仮接着し、乾燥機で１８０℃×１２０分間硬化させ、試料Ａとした。
【００６３】
また、得られた耐熱性樹脂組成物を厚さ２５μｍのポリイミドフィルム（東レ・デュポン(株)製商品名：カプトン１００Ｈ）に乾燥後の膜厚が２０μｍになるように塗布し、１３０℃で３分間乾燥させたものを作製して、乾燥機で１８０℃×１２０分間硬化させ、試料Ｂとした。
【００６４】
また、得られた耐熱性樹脂組成物を厚さ５０μｍのテフロンフィルム（日東電工(株)製商品名：ナフロンテープＴＯＭＢＯ９００１）に乾燥後の膜厚が２０μｍになるように塗布し、１３０℃で３分間乾燥させたものを作製して、乾燥機で１８０℃×１２０分間硬化させ、テフロンフィルム付き接着フィルムを得、テフロンフィルムを剥がして試料Ｃとした。
【００６５】
これら試料を用いて、接着性（試料Ａ）、はんだ耐熱性（試料Ａ）、難燃性 （試料Ｂ）、ガラス転移点（試料Ｃ）、及び貯蔵弾性率（試料Ｃ）を測定しその結果を表３に示した。これら特性の測定方法、条件を次に示す。
【００６６】
（接着性）
試料Ａ（試料構成：ポリイミドフィルム／耐熱性樹脂組成物／圧延銅箔粗化面）を用いて９０°方向及び１８０°方向の引き剥がし試験を下記条件で行い、ポリイミドフィルム及び銅箔粗化面との剥離強度（kN/m）を測定した。
測定温度：２５℃、剥離速度：５０mm/min
【００６７】
（はんだ耐熱性）
試料Ａ（試料構成：ポリイミドフィルム／耐熱性樹脂組成物／圧延銅箔粗化面）を用いて３００℃のはんだ浴に３分間、試料を浸漬し、ふくれ、はがれ等の外観異常の有無を調べた。
○：ふくれ、はがれ等の外観異常有り
×：ふくれ、はがれ等の外観異常無し
【００６８】
（難燃性）
試料Ｂ（試料構成：ポリイミドフィルム／樹脂組成物）を用いてＵＬ９４難燃性規格に準拠して難燃性グレードを測定した。
【００６９】
（ガラス転移点及び貯蔵弾性率）
試料Ｃ（試料構成：耐熱性樹脂組成物のみ）を用いて動的粘弾性測定（レオメトリック(株)製商品名：）を下記条件で行った。ガラス転移点（Ｔｇ）はtanδピークの最大値を用いた。
測定モード：引張り
チャック間距離：２２．５mm
測定温度：−５０〜３００℃
昇温速度：５℃／分
測定周波数：１０Hz
試料サイズ：５mm幅×３０mm長
【００７０】
（比較例１）
比較例１として、実施例１〜４の配合で（Ｂ）ゴム系エラストマーを含まない配合とした。そして、実施例と同様にして試料を作製し、諸特性を測定した結果を表３に示した。
【００７１】
（比較例２）
比較例２として、実施例１〜４の配合で（Ｄ）熱硬化性樹脂を含まない配合とした。そして、実施例と同様にして試料を作製し、諸特性を測定した結果を表３に示した。
【００７２】
（比較例３）
比較例３として、実施例１〜４の耐熱性樹脂組成物の代わりにメラミン樹脂 （三井サイテック社製、サイメル３０３）を使用した。そして、実施例と同様にして試料を作製し、諸特性を測定した結果を表３に示した。
【００７３】
【表３】
【発明の効果】
請求項１記載の耐熱性樹脂組成物は、接着性及び耐熱性に優れ、各種プリント配線板、半導体パッケージ用接着剤、接着フィルム、半導体パッケージ用封止材に好適である。請求項２記載の耐熱性樹脂組成物は、請求項１記載の発明の効果に加えて、さらに非ハロゲン系で十分な難燃性、接着性及び耐熱性に優れ、各種プリント配線板、半導体パッケージ用接着剤、接着フィルム、半導体パッケージ用封止材に好適である。
【００７５】
請求項３記載の接着フィルムは、非ハロゲン系で十分な難燃性、接着性及び耐熱性に優れ、各種プリント配線板、半導体パッケージ用に有用である。請求項４記載の接着層付ポリイミドフィルムは、非ハロゲン系で十分な難燃性、接着性及び耐熱性に優れ、各種プリント配線板、半導体パッケージ用に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a heat resistant resin composition, an adhesive film using the same, and a polyimide film with an adhesive layer.
[0002]
[Prior art]
In recent years, with the rapid progress of miniaturization and weight reduction of various electronic devices, the mounting density of electronic components has increased, and the characteristics required for wiring boards, semiconductor packages and the like used therein have also diversified. Under these circumstances, printed wiring boards require smaller and higher-density wiring areas, such as multilayer wiring boards (build-up wiring boards), flexible wiring boards (FPC), and flexible rigid wiring boards (FRC). Is increasing. These wiring boards use various adhesives or adhesive films in the manufacturing process, but have excellent adhesiveness and heat resistance, and are environmentally friendly non-halogen adhesives that have sufficient flame retardancy Or there was no adhesive film.
[0003]
In addition, semiconductor packages are rapidly becoming smaller, lighter, and higher in density, and their development is remarkable, but various polyimide films are widely used as materials therein. There were no non-halogen-based adhesives and sealing materials that were excellent in adhesion to the polyimide film, had good heat resistance, and were environmentally friendly.
[0004]
Conventional heat-resistant resin compositions that use the so-called “free radical trapping effect” or the dehydration carbonization action of antimony oxyhalide by combining a halogen compound and an antimony compound are widely known. The problem of environmental pollution that emits toxic substances such as dioxins during combustion has not been solved.
[0005]
[Problems to be solved by the invention]
Claim 1 The described invention provides a heat-resistant resin composition that is excellent in adhesiveness and heat resistance and is suitable for various printed wiring boards, adhesives for semiconductor packages, adhesive films, and sealing materials for semiconductor packages. Claim 2 The described invention is claimed. 1 In addition to the effects of the invention described above, it is non-halogen and has excellent flame resistance, adhesion and heat resistance, and is suitable for various printed wiring boards, adhesives for semiconductor packages, adhesive films, and sealing materials for semiconductor packages. A heat resistant resin composition is provided.
[0006]
Claim 3 The described invention provides an adhesive film which is non-halogen and excellent in sufficient flame retardancy, adhesiveness and heat resistance, and is useful for various printed wiring boards and semiconductor packages. Claim 4 The described invention provides a polyimide film with an adhesive layer that is non-halogen and excellent in sufficient flame retardancy, adhesion, and heat resistance, and is useful for various printed wiring boards and semiconductor packages.
[0007]
[Means for Solving the Problems]
The present invention comprises (A) a siloxane-modified polyamideimide resin, (B) epoxidation Poly The present invention relates to a heat resistant resin composition containing butadiene and (C) an epoxy resin.
[0008]
In addition, the present invention provides (A) the following general formula (I) obtained by reacting a mixture of a diamine having 3 or more aromatic rings and a siloxane diamine and trimellitic anhydride with a siloxane-modified polyamideimide resin. The heat-resistant resin composition is a siloxane-modified polyamideimide resin obtained by reacting a mixture containing a diimidedicarboxylic acid represented by the general formula (II) and an aromatic diisocyanate represented by the following general formula (III): .
[0009]
[Chemical 8]
[Chemical 9]
[0010]
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[0011]
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[0012]
Ma The present invention further relates to the heat-resistant resin composition further comprising (D) a phosphorus compound or (E) an inorganic filler.
[0013]
Moreover, this invention relates to the adhesive film which consists of the said heat resistant resin composition.
Moreover, it is related with the polyimide film with an adhesive layer by which the said adhesive film was laminated | stacked as an adhesive layer on a polyimide film.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, and (meth) acrylate means acrylate and methacrylate corresponding thereto.
[0015]
The heat resistant resin composition of the present invention comprises (A) a siloxane-modified polyamideimide resin, (B) a rubber-based elastomer and (C) a thermosetting resin.
[0016]
The (A) siloxane-modified polyamideimide resin is obtained by reacting a mixture of a diamine having three or more aromatic rings and a siloxane diamine with trimellitic anhydride, and the general formula (I) and the general formula (II). It is preferable that it is a siloxane modified polyamidoimide resin obtained by making the mixture containing the diimide dicarboxylic acid represented by these, and the aromatic diisocyanate represented by the said general formula (III) react.
[0017]
In the general formula (II), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert- Butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl , Nonadecyl group, icosyl group, structural isomers thereof, and the like.
In the general formula (II), examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. A group, a nitro group, a cyano group, a mercapto group, an allyl group, an alkyl group having 1 to 20 carbon atoms, or the like.
[0018]
Examples of the diamine having three or more aromatic rings include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP), bis [4- (3-aminophenoxy). Phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-aminophenoxy) Biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4 -Aminophenoxy) benzene and the like. From the viewpoint of balance of properties and cost of siloxane-modified polyamideimide resin, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane (BAPP) is preferred. These may be used alone or in combination of two or more.
[0019]
As the siloxane diamine used in the present invention, a known siloxane diamine can be used.
Embedded image
[0020]
Examples of the divalent organic group in the general formula (IV) include alkylene groups such as methylene group, ethylene group and propylene group, and arylene groups such as phenylene group, tolylene group and xylylene group.
[0021]
Examples of such siloxane diamine include those represented by the following formula.
[0022]
Examples of commercially available compounds include amino-modified silicone oil X-22-161AS (amine equivalent 450, trade name of Shin-Etsu Chemical Co., Ltd.), X-22, which is a siloxane-based both-end amine among these. -161A (amine equivalent 840, trade name manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-161B (amine equivalent 1500, product name manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-853 (amine equivalent 650, Toray Dow Corning) Silicone Co., Ltd. trade name), BY16-853B (amine equivalent 2200, Toray Dow Corning Silicone Co., Ltd. trade name), and the like.
[0023]
Examples of the aromatic diisocyanate represented by the general formula (III) include 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene- Examples thereof include 1,5-diisocyanate and 2,4-tolylene dimer, and 4,4'-diphenylmethane diisocyanate (MDI) is preferable from the viewpoint of imparting flexibility and preventing crystallinity. These may be used alone or in combination of two or more.
From the viewpoint of heat resistance, aliphatic diisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate are used in combination in an amount of about 5 to 10 mol% with respect to the aromatic diisocyanate. be able to.
[0024]
From the viewpoint of heat resistance, in addition to the diimidecarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, phthalic acid and naphthalenedicarboxylic acid, fats such as adipic acid, sebacic acid, decanedioic acid, dodecanedioic acid and dimer acid A group dicarboxylic acid or the like can be used in combination at about 5 to 10 mol% with respect to the diimidecarboxylic acid.
[0025]
The (A) component siloxane-modified polyamideimide resin used in the present invention is, for example, a mixture of diamine (1) having three or more aromatic rings and siloxane diamine (2) ((1) / (2) = 0.1). /99.9 to 99.9 / 0.1 molar ratio) and trimellitic anhydride (hereinafter abbreviated as TMA) ((1) + (2)) and the molar ratio of TMA is 1/2. .20 to 1 / 2.05 in the presence of an aprotic polar solvent at 50 to 90 ° C. for about 0.2 to 1.5 hours, and further, an aromatic hydrocarbon azeotroped with water is removed. The aromatic diimide dicarboxylic acid represented by the above general formula (I) and the above general formula (II) are added at about 0.1 to 0.5% by weight of the protic polar solvent and reacted at 120 to 180 ° C. To produce a mixture containing siloxane diimide dicarboxylic acid represented by Reaction with the aromatic diisocyanate (3) represented by the formula (III) at about 150 to 250 ° C. for about 0.5 to 3 hours [((1) + (2)) / (3) = 1 / 1.50 ~ 1 / 1.05 molar ratio].
[0026]
Moreover, after manufacturing an aromatic diimide dicarboxylic acid, the aromatic hydrocarbon is removed from the solution by bringing the solution to about 150 to 250 ° C., and the reaction is performed with an aromatic diisocyanate. You can also.
The siloxane-modified polyamideimide resin is preferably a varnish containing an aprotic polar solvent.
[0027]
The mixing ratio of the mixture of the diamine (1) having three or more aromatic rings and the siloxane diamine (2) is (1) / (2) = 0.1 / 99.9 to 99.9 / 0.1. The molar ratio is preferably 0.1 / 99.9 to 70.0 / 30.0 molar ratio. If this molar ratio is less than 0.1 / 99.9, the molecular weight of the obtained resin tends to decrease, and if it exceeds 99.9 / 1, the resin skeleton of the obtained resin tends to be rigid.
[0028]
Furthermore, the molar ratio for obtaining the mixture containing the diimide dicarboxylic acid represented by the general formula (I) and the general formula (II) is ((1)) by reacting the above mixture with trimellitic anhydride (TMA). + (2)) / TMA = 1 / 2.20 to 1 / 2.05, more preferably 1 / 2.15 to 1 / 2.10. If this molar ratio is less than 1 / 2.20, TMA remains, and the molecular weight of the finally obtained resin tends to decrease. If it exceeds 1 / 2.05, diamine remains, and the resin finally obtained The molecular weight tends to decrease.
[0029]
Next, the mixture of the diimide dicarboxylic acid represented by the general formula (I) and the general formula (II) is reacted with the aromatic diisocyanate (3) represented by the general formula (III) to obtain a siloxane-modified polyamideimide resin. Is preferably ((1) + (2)) / (3) = 1 / 1.50 to 1 / 1.05, preferably 1 / 1.4 to 1 / 1.1. It is more preferable that If this molar ratio is less than 1 / 1.50, the molecular weight of the resulting resin tends to decrease, and if it exceeds 1 / 1.05, the molecular weight of the resulting resin tends to decrease.
[0030]
The aprotic polar solvent is preferably an organic solvent that does not react with diamine having three or more aromatic rings, siloxane diamine, and TMA, and examples thereof include dimethylacetamide, dimethylformamide, dimethylsulfoxide, and N-methyl-2. -Pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone and the like. Since the imidization reaction requires high temperature, N-methyl-2-pyrrolidone having a high boiling point is more preferable. These may be used alone or in combination of two or more.
[0031]
The amount of water contained in these aprotic polar solvents is preferably 0.1 to 0.2% by weight. When the water content exceeds 0.2% by weight, the trimellitic acid produced by hydration of TMA does not sufficiently advance the reaction, and the molecular weight of the polymer tends to decrease. The amount of the aprotic polar solvent used in the present invention is 10 to 70% by weight based on the total amount of the diamine having three or more aromatic rings, siloxane diamine, trimetic anhydride and the aprotic polar solvent. It is preferable to be in the range. If the amount used is less than 10%, the solubility of TMA tends to be lowered and sufficient reaction cannot be performed. If it exceeds 70% by weight, it tends to be disadvantageous as an industrial production method.
[0032]
Examples of the aromatic hydrocarbon include toluene, xylene and the like.
[0033]
(A) The weight average molecular weight of the siloxane-modified polyamideimide resin is preferably 20,000 to 300,000, more preferably 25,000 to 200,000, and 30,000 to 150,000. It is particularly preferred. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography method, and is converted with the analytical curve created using standard polystyrene.
[0034]
Examples of the rubber-based elastomer (B) in the present invention include acrylonitrile rubber, polybutadiene rubber, acrylic-butadiene rubber, and silicone rubber. These may be used alone or in combination of two or more. Examples of the acrylic rubber include copolymers of acrylonitrile and other (meth) acrylic monomers, and epoxy-modified products thereof. For example, copolymers with glycidyl acrylate, Etoto manufactured by Toto Kasei Co., Ltd. YR528, YR570, etc. are mentioned.
[0035]
Examples of the polybutadiene rubber include butadiene rubber, butadiene-isoprene rubber, butadiene-styrene rubber, epoxy modified products thereof, and the like. For example, epoxidized polybutadiene, epolide PB3600, PB4700 manufactured by Daicel Chemical Industries, Ltd., for example. And epoxidized butadiene-styrene. From the viewpoint of adhesiveness and heat resistance, it is preferably an epoxy-modified product, more preferably Epolide PB3600.
[0036]
Examples of the acrylic-butadiene rubber include acrylonitrile-butadiene (NBR rubber), acrylic-isoprene, acrylic-butadiene-isoprene, acrylic-butadiene-styrene, carboxylic acid-modified products thereof, epoxy-modified products thereof, and the like. For example, B.I. F. Goodrich's hiker, Nippon Synthetic Rubber's XER-81, XER-91, PNR-1H, Toto Kasei's Epotot YR450, YR207, and the like.
[0037]
The silicone rubber is preferably composed mainly of organopolysiloxane, for example, polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, partly modified with vinyl group, alkoxy group, etc. And epoxy-modified products such as SY430 manufactured by Wacker, SH6040 manufactured by Toray Dow Corning Silicone, and the like.
[0038]
Among these above-mentioned epoxy modified products, PB3600 is particularly preferable from the viewpoint of adhesiveness and heat resistance.
[0039]
Examples of the thermosetting resin (C) in the present invention include an epoxy resin, a phenol resin, and a polyester resin. , Bi Examples thereof include a maleimide triazine resin. Epoxy resins are preferred from the standpoint of adhesiveness and handleability. For example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthalene type epoxy resins. And its modified product, bixylenyl diglycidyl ether, YDC1312 (manufactured by Tohto Kasei Co., Ltd.), Epototo YD-8125 (manufactured by Tohto Kasei Co., Ltd.), TMH574 (manufactured by Sumitomo Chemical Co., Ltd.), Epikote 1031S (oiled shell epoxy ( Aromatic epoxy resins such as neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrahydrophthalic acid diglycidyl ester, etc., triglycidyl isocyanate And heterocyclic epoxy compounds such as nates.
[0040]
In these, it is preferable to use the epoxy resin which has a 2 or more glycidyl group, and its hardening accelerator. Further, the more glycidyl groups are more preferable, and 3 or more are particularly preferable. The blending amount varies depending on the number of glycidyl groups, and the more glycidyl groups, the smaller the blending amount with respect to the siloxane-modified polyamideimide resin. Further, it is more preferable to use an epoxy resin curing agent in combination.
[0041]
The curing accelerator and curing agent are not particularly limited as long as they react with an epoxy resin or accelerate curing, and examples thereof include amines, imidazoles, polyfunctional phenols, and acid anhydrides. It is done.
Examples of the amines include dicyandiamide, diaminodiphenylmethane, guanylurea and the like.
Examples of the imidazoles include alkyl group-substituted imidazoles such as 2-ethyl-4-methylimidazole and benzimidazoles.
Examples of the polyfunctional phenols include hydroquinone, resorcinol, bisphenol A and their halogen compounds, novolak phenol type phenol resins and resole type phenol resins which are addition condensates of the polyfunctional phenols and formaldehyde. .
Examples of the acid anhydrides include phthalic anhydride, benzophenone tetracarboxylic acid dihydrate, and methyl hymic acid. From the viewpoint of reactivity and pot life, imidazoles or amines are used. This is particularly preferred.
These may be used alone or in combination of two or more.
[0042]
Examples of the phosphorus compound (D) contained as necessary in the present invention include triphenyl phosphate, triglycidyl phosphate, polyphosphate compound, resorcin polyphosphate compound, trixylate. And organic phosphorus compounds such as phosphoric acid esters such as nyl phosphate, aromatic condensed phosphoric acid ester and biphenyl type phosphoric acid ester (trade name CR-747 manufactured by Daihachi Chemical Industry Co., Ltd.). .
[0043]
Examples of the (E) inorganic filler contained as necessary in the present invention include aluminum hydroxide (trade name Hygielite H-42STE, etc. manufactured by Showa Denko KK), magnesium hydroxide (Kyowa Chemical Industry Co., Ltd.). (Trade name: Kisuma 5PH), calcium aluminate, silicone polymer powder and the like, and aluminum hydroxide or magnesium hydroxide containing crystal water is more preferable. These may be used alone or in combination of two or more.
[0044]
In order to further improve the flame retardancy, it is preferable to use a phosphorus compound as the component (D) and an inorganic filler as the component (E) in combination.
[0045]
The blending amount of the (B) rubber-based elastomer in the present invention is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the (A) siloxane-modified polyamideimide resin from the viewpoint of adhesiveness, flexibility and heat resistance. 7 to 12 parts by weight is particularly preferable. If the blending amount is less than 5 parts by weight, the adhesiveness tends to decrease, and if it exceeds 20 parts by weight, the solder heat resistance, adhesiveness and glass transition temperature tend to decrease.
[0046]
The blending amount of the (C) thermosetting resin in the present invention is 10 to 150 parts by weight with respect to 100 parts by weight of the (A) siloxane-modified polyamideimide resin from the viewpoint of adhesiveness, flexibility and heat resistance. It is preferably 30 to 70 parts by weight. If the blending amount is less than 10 parts by weight, the crosslink density of the cured product tends to decrease and the insulating property tends to be inferior. There is a tendency to decrease.
[0047]
In the present invention, the compounding amount of the curing accelerator or curing agent contained as necessary is preferably such that in the case of amines, the equivalent of the active hydrogen of the amine and the epoxy equivalent of the epoxy resin are approximately equal. In the case of imidazoles, the amount is preferably 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the epoxy resin. In the case of polyfunctional phenols, it is preferably 0.6 to 1.2 hydroxyl group equivalents per 1 epoxy group equivalent of the epoxy resin. If the blending amount is less than the above blending amount, the uncured epoxy resin remains and Tg tends to be low. There is a tendency to decrease.
[0048]
The blending amount of the phosphorus compound (D) contained as necessary in the present invention is 5 to 25 parts by weight with respect to 100 parts by weight of the total amount of the components (A) + (B) + (C). Preferably, it is 10 to 15 parts by weight. When the blending amount is less than 5 parts by weight, the flame retardancy tends to be insufficient, and when it exceeds 25 parts by weight, the adhesiveness and the solder heat resistance tend to decrease.
[0049]
In the present invention, the blending amount of the (E) inorganic filler contained as necessary is 50 to 80 parts by weight with respect to 100 parts by weight of the total amount of the components (A) + (B) + (C). Preferably, it is 50-60 weight part. If the blending amount is less than 50 parts by weight, the flame retardancy tends to decrease, and if it exceeds 80 parts by weight, the adhesion and solder heat resistance tend to decrease.
[0050]
In the present invention, these compositions are preferably mixed in an organic solvent to obtain a heat resistant resin composition having a solid content of about 30 to 40% by weight.
The organic solvent is not particularly limited as long as solubility is obtained, and examples thereof include dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, and cyclohexanone. .
[0051]
In addition to the above components, the heat-resistant resin composition of the present invention appropriately contains a dispersant (Disperbyk110, etc.), a coupling agent, a pigment, a leveling agent, an antifoaming agent, an ion trapping agent, and the like as necessary. You may do it.
[0052]
In order to form an adhesive layer using the heat resistant resin composition of the present invention, for example, it may be applied as it is to form an adhesive layer, or a layer of the heat resistant resin composition is laminated in the form of an adhesive film. By doing so, an adhesive layer may be formed. Moreover, when using an adhesive film, after laminating, you may remove the following support base material, and you may remove before laminating | stacking.
[0053]
The adhesive film of the present invention can be produced, for example, by applying a heat resistant resin composition dissolved in a predetermined organic solvent on a supporting substrate and then drying the solvent by heating or hot air blowing.
Examples of the support substrate include polyolefin such as polyethylene and polyvinyl chloride, polyester such as polyethylene terephthalate, polycarbonate, Teflon film, release paper, copper foil, metal foil such as aluminum foil, and the like. The thickness of the supporting substrate is preferably 10 to 150 μm. In addition, you may perform a mud process, a corona process, a mold release process, etc. to a support base material.
The organic solvent is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, and butyl cellosolve. And the like, carbitols such as carbitol and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or in combination of two or more.
[0054]
The thickness of the heat-resistant resin composition laminated on the support substrate is preferably 5 to 50 μm, and more preferably 10 to 40 μm.
Examples of the form of the adhesive film include a sheet shape and a roll shape that are cut by a certain length. From the standpoint of storage stability, productivity, and workability, it is preferable to further laminate a protective film on the surface opposite to the heat resistant resin composition, and roll and store it.
Examples of the protective film include polyolefins such as polyethylene, polyvinyl chloride, and polypropylene, polyesters such as polyethylene terephthalate, and release papers as in the case of the supporting substrate. The thickness of the protective film is preferably 10 to 100 μm. In addition, you may perform a mud process, an embossing process, and a mold release process to a protective film.
[0055]
For example, the adhesive film of the present invention can be made into a polyimide film with an adhesive layer by laminating it on a polyimide film or the like, and can be made into a substrate for a flexible printed wiring board by laminating a metal foil.
[0056]
【Example】
The present invention will be specifically described below with reference to examples.
[0057]
(Synthesis Example 1)
BAPP (2,2-bis [4] as a diamine having 3 or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer. -(4-aminophenoxy) phenyl] propane), reactive silicone oil X-22-161-AS (trade name, amine equivalent 416 manufactured by Shin-Etsu Chemical Co., Ltd.), siloxane diamine, TMA (trimellitic anhydride), NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent was charged at a blending ratio shown in Table 1 and stirred at 80 ° C. for 30 minutes. Then, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, the temperature was raised, and the mixture was refluxed at 160 ° C. for 2 hours.
[0058]
Confirm that water has accumulated about 3.6 ml or more in the moisture determination receiver and that no water has flowed out. The temperature was raised to remove toluene.
Thereafter, the solution was returned to room temperature, MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate was added in the amount shown in Table 1, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution A-1 of a siloxane-modified polyamideimide resin was obtained.
[0059]
[Table 1]
(Examples 1-4)
The materials shown in Table 2 are blended with the siloxane-modified polyamideimide resin A-1 obtained in Synthesis Example 1, and after stirring for 1 hour until the resin becomes uniform, the inorganic filler and the resin are further uniform. The mixture was kneaded with three rolls and allowed to stand at room temperature for 24 hours for defoaming to obtain a heat resistant resin composition.
[0061]
[Table 2]
In addition, the obtained heat-resistant resin composition was applied to a Teflon film having a thickness of 50 μm (trade name: Naflon tape TOMBO9001 manufactured by Nitto Denko Corporation) so that the film thickness after drying was 20 μm. The product was dried for 1 minute and cured with a dryer at 180 ° C. for 120 minutes to obtain an adhesive film. A 25 μm-thick polyimide film (trade name: Kapton, manufactured by Toray DuPont Co., Ltd.) was used. 100H) The heat-resistant resin composition layer was laminated on the surface, and the Teflon film was removed. Next, the roughened surface side of 35 μm rolled copper foil (trade name: BHY-22B-T, manufactured by Nikko Gould Wheel Co., Ltd.) is bonded together, and the temperature is 120 ° C. and the pressure is 5 kgf / cm. 2 Was subjected to hot roll laminating and temporarily bonded, and then cured at 180 ° C. for 120 minutes with a dryer to obtain sample A.
[0063]
Further, the obtained heat-resistant resin composition was applied to a polyimide film having a thickness of 25 μm (trade name: Kapton 100H, manufactured by Toray DuPont Co., Ltd.) so that the film thickness after drying was 20 μm, and the coating was made at 130 ° C. 3 A sample dried for minutes was prepared and cured at 180 ° C. for 120 minutes with a dryer to obtain Sample B.
[0064]
In addition, the obtained heat-resistant resin composition was applied to a Teflon film having a thickness of 50 μm (trade name: Naflon tape TOMBO9001 manufactured by Nitto Denko Corporation) so that the film thickness after drying was 20 μm. What was dried for a minute was produced, it was made to harden | cure 180 degreeC x 120 minutes with a dryer, the adhesive film with a Teflon film was obtained, the Teflon film was peeled off, and it was set as the sample C.
[0065]
Using these samples, the adhesion (sample A), solder heat resistance (sample A), flame retardancy (sample B), glass transition point (sample C), and storage modulus (sample C) were measured, and the results Are shown in Table 3. The measurement method and conditions for these characteristics are shown below.
[0066]
(Adhesiveness)
Using sample A (sample composition: polyimide film / heat-resistant resin composition / rolled copper foil roughened surface), the peeling test in the 90 ° direction and 180 ° direction was conducted under the following conditions, and the polyimide film and copper foil roughened surface: The peel strength (kN / m) was measured.
Measurement temperature: 25 ° C., peeling speed: 50 mm / min
[0067]
(Solder heat resistance)
Using sample A (sample composition: polyimide film / heat-resistant resin composition / rolled copper foil roughened surface), immerse the sample in a 300 ° C. solder bath for 3 minutes, and check for abnormal appearance such as blistering and peeling. It was.
○: Appearance abnormalities such as blistering and peeling
×: No appearance abnormality such as blistering or peeling
[0068]
(Flame retardance)
Using sample B (sample configuration: polyimide film / resin composition), the flame retardancy grade was measured in accordance with UL94 flame retardancy standards.
[0069]
(Glass transition point and storage modulus)
Using sample C (sample configuration: heat resistant resin composition only), dynamic viscoelasticity measurement (trade name: manufactured by Rheometric Co., Ltd.) was performed under the following conditions. The maximum value of the tan δ peak was used as the glass transition point (Tg).
Measurement mode: Tensile
Distance between chucks: 22.5mm
Measurement temperature: -50 to 300 ° C
Temperature increase rate: 5 ° C / min
Measurement frequency: 10Hz
Sample size: 5mm width x 30mm length
[0070]
(Comparative Example 1)
As comparative example 1, it was set as the mixing | blending which does not contain the (B) rubber-type elastomer by the mixing | blending of Examples 1-4. And the sample was produced like Example and the result of having measured various characteristics was shown in Table 3.
[0071]
(Comparative Example 2)
As comparative example 2, it was set as the mixing | blending which does not contain (D) thermosetting resin by the mixing | blending of Examples 1-4. And the sample was produced like Example and the result of having measured various characteristics was shown in Table 3.
[0072]
(Comparative Example 3)
As Comparative Example 3, a melamine resin (manufactured by Mitsui Cytec Co., Ltd., Cymel 303) was used instead of the heat-resistant resin compositions of Examples 1 to 4. And the sample was produced like Example and the result of having measured various characteristics was shown in Table 3.
[0073]
[Table 3]
【The invention's effect】
Claim 1 The mounted heat-resistant resin composition is excellent in adhesiveness and heat resistance, and is suitable for various printed wiring boards, adhesives for semiconductor packages, adhesive films, and sealing materials for semiconductor packages. Claim 2 The heat-resistant resin composition described in claim 1 In addition to the effects of the invention described above, it is non-halogen and has excellent flame resistance, adhesion and heat resistance, and is suitable for various printed wiring boards, adhesives for semiconductor packages, adhesive films, and sealing materials for semiconductor packages. It is.
[0075]
Claim 3 The described adhesive film is non-halogen-based and has excellent flame retardancy, adhesiveness and heat resistance, and is useful for various printed wiring boards and semiconductor packages. Claim 4 The described polyimide film with an adhesive layer is non-halogen and excellent in flame retardancy, adhesiveness and heat resistance, and is useful for various printed wiring boards and semiconductor packages.
Claims (4)
前記（Ａ）シロキサン変性ポリアミドイミド樹脂が、芳香族環を３個以上有するジアミン及びシロキサンジアミンの混合物と無水トリメリット酸とを反応させて得られる下記一般式（Ｉ）及び下記一般式（II）で表されるジイミドジカルボン酸を含む混合物と下記一般式（III）で表される芳香族ジイソシアネートとを反応させて得られるシロキサン変性ポリアミドイミド樹脂である耐熱性樹脂組成物。
The (A) siloxane-modified polyamideimide resin is obtained by reacting a mixture of a diamine having three or more aromatic rings and a siloxane diamine with trimellitic anhydride, and the following general formulas (I) and (II): A heat-resistant resin composition, which is a siloxane-modified polyamideimide resin obtained by reacting a mixture containing a diimidedicarboxylic acid represented by formula (II) with an aromatic diisocyanate represented by the following general formula (III).
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| JP16032099A JP4378577B2 (en) | 1999-06-08 | 1999-06-08 | Heat resistant resin composition, adhesive film using the same, and polyimide film with adhesive layer |
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| Application Number | Priority Date | Filing Date | Title |
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| JP16032099A JP4378577B2 (en) | 1999-06-08 | 1999-06-08 | Heat resistant resin composition, adhesive film using the same, and polyimide film with adhesive layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4671083B2 (en) * | 2000-11-28 | 2011-04-13 | 日立化成工業株式会社 | Thermosetting heat resistant adhesive film |
| JP2003003134A (en) * | 2001-06-20 | 2003-01-08 | Japan Gore Tex Inc | IC chip bonding sheet and IC package |
| KR100676335B1 (en) | 2001-09-05 | 2007-02-02 | 히다치 가세고교 가부시끼가이샤 | Flame retardant heat resistant resin composition, adhesive film using the same |
| JP2004323807A (en) * | 2003-04-23 | 2004-11-18 | Hitachi Kasei Polymer Co Ltd | Flame retardant adhesive composition and cover lay |
| WO2005007756A1 (en) | 2003-05-21 | 2005-01-27 | Hitachi Chemical Co., Ltd. | Primer, conductor foil with resin, laminate and process for producing the laminate |
| JP4639752B2 (en) * | 2004-10-22 | 2011-02-23 | 日立化成工業株式会社 | Circuit board with adhesive layer, method for producing multilayer printed wiring board, and multilayer printed wiring board |
| JP4507874B2 (en) * | 2004-12-20 | 2010-07-21 | 住友ベークライト株式会社 | Resin composition, prepreg and laminate |
| JP6202677B2 (en) * | 2013-12-25 | 2017-09-27 | 住友電工プリントサーキット株式会社 | Heat-resistant printed wiring board for pressure sensor, pressure sensor module and pressure sensor |
| WO2017153576A1 (en) * | 2016-03-11 | 2017-09-14 | Epg (Engineered Nanoproducts Germany) Ag | Materials for use as adhesive and for surface sealing |
| WO2019123562A1 (en) * | 2017-12-20 | 2019-06-27 | 日立化成株式会社 | Polyamide imide resin, polyamide imide resin composition, and semiconductor device using same |
| CN111849388B (en) * | 2020-07-31 | 2021-09-28 | 南京大学 | High-voltage-resistant insulating non-drying waterproof sealant |
| CN114426674B (en) * | 2021-12-10 | 2023-02-24 | 哈尔滨理工大学 | Preparation method and application of thermosetting resin-based toughened high-thermal-conductivity filler |
| CN114381051B (en) * | 2022-01-13 | 2023-05-16 | 张守保 | Heat-conducting insulating composite material and preparation method thereof |
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