JP2004341058A - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- JP2004341058A JP2004341058A JP2003134776A JP2003134776A JP2004341058A JP 2004341058 A JP2004341058 A JP 2004341058A JP 2003134776 A JP2003134776 A JP 2003134776A JP 2003134776 A JP2003134776 A JP 2003134776A JP 2004341058 A JP2004341058 A JP 2004341058A
- Authority
- JP
- Japan
- Prior art keywords
- group
- film
- resin composition
- alkyl group
- carbon atoms
- 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.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000000962 organic group Chemical group 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000000243 solution Substances 0.000 abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 10
- 229920001721 polyimide Polymers 0.000 abstract description 10
- 238000011161 development Methods 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 239000004642 Polyimide Substances 0.000 abstract description 6
- 239000004020 conductor Substances 0.000 abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- -1 alkoxyalkyl ester Chemical class 0.000 description 97
- 239000010408 film Substances 0.000 description 70
- 229920005575 poly(amic acid) Polymers 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000002966 varnish Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 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 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000013039 cover film Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 150000004292 cyclic ethers Chemical class 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002788 crimping Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 101150059062 apln gene Proteins 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- AWOATHYNVXCSGP-UHFFFAOYSA-M (4-methylphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 AWOATHYNVXCSGP-UHFFFAOYSA-M 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- QMGJMGFZLXYHCR-UHFFFAOYSA-N 1-(2-butoxypropoxy)butane Chemical compound CCCCOCC(C)OCCCC QMGJMGFZLXYHCR-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-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
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- AVMSWPWPYJVYKY-UHFFFAOYSA-N 2-Methylpropyl formate Chemical compound CC(C)COC=O AVMSWPWPYJVYKY-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000006228 2-isobutoxyethyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000006227 2-n-butoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
ポリアミド酸のアルコキシアルキルエステルを主成分とする感光性樹脂組成物に関し、更に詳しくは該感光性樹脂組成物を用いたドライフィルムに関する。
【０００２】
【従来技術】
近年の「マルチメディア」社会において、全地球規模での情報量の急速な増大化で、情報データの交換、伝送に大容量化・高速化・デジタル化が要求されている。これらの要求に対し、電子情報システム、デバイスの大集積化・高速化が進行するとともに電子情報機器の高性能・高機能化（複合化・融合化）と携帯化（高密度化）の動きが激しくなってきている。
【０００３】
これら電子情報機器と半導体デバイスのインターフェイスとなる「実装技術」は、高密度化に向けてその重要性が世の中において益々認識されてきた。この「実装技術」の中で主役を演じている半導体デバイスと並び今日注目されてきているのが半導体用パッケージであり、その関連技術の技術確立が急がれている。
【０００４】
最近、導体回路パターンの微細化と位置精度の向上、更に実装部品の小型化、ＩＣパッケージのリードのファインピッチ化により層間絶縁膜、ソルダーレジスト皮膜等の絶縁皮膜形成も画像精度や位置精度の向上を必要としてきている。従って、近年では精度よく皮膜形成ができる方法として上記フォト法を用いて層間絶縁膜ソルダーレジスト皮膜や絶縁皮膜を形成する方法が広く採用されるようになった。
【０００５】
上記フォト法では、所望の厚みに感光性樹脂組成物を基材に塗布した後乾燥して感光性皮膜を形成し、この感光性皮膜にネガのフォトマスクを乗せて、紫外線等の活性光線で露光焼付けを行うことが一般的である。感光性皮膜は、フォトマスクの透明部分を透過した活性光線で硬化し、未露光部分は現像液で除去される。上記フォト法で形成された感光性皮膜は更に熱や活性光線で硬化し、ソルダーレジスト皮膜や絶縁皮膜になる。形成された画像はフォトマスクに極めて近い精度で形成できるため、微細な画像や位置精度を容易に得ることができる。
【０００６】
しかしこの方法では、上記の如く基材表面に塗布、溶剤乾燥工程が必要であり、ＦＰＣ製造上工程が煩雑になり、またピンホールや異物による不良率の低減に苦慮しているのが実情であった。そこでアルカリ水溶液現像型のネガ型層間絶縁膜やフォトソルダーレジストフィルムの研究が近年盛んとなり、例えば、特公昭５６−４０３２９公報には、エポキシ樹脂に不飽和モノカルボン酸を付加させ更に多塩基酸無水物を付加させてなる反応生成物をベースポリマーとする感光性樹脂組成物が開示されている。特開昭６１−２４３８６９公報には、ノボラック型エポキシアクリレート等に多塩基酸無水物を付加させた反応生成物をベースポリマーとし、アルカリ水溶液を現像液とするフォトソルダーレジスト組成物が開示されている。しかしながら、上記の組成物で得られるソルダーレジスト皮膜は、耐熱性、耐溶剤性や耐薬品性において不十分であり、絶縁性、誘電率に関する特性も十分とは言えない。またネガ型であるがために、耐薬品性向上が難しく、微細回路の形成が困難であり、薄型ＢＧＡ等への適用はできなかった。
【０００７】
一方ポリイミド前駆体であるポリアミド酸を加熱処理することによって得られるポリイミドが、その優れた耐熱性、耐薬品性、誘電特性等から、ＩＣ保護膜、層間絶縁膜として使用されており、更に露光，現像により直接パターンが形成できる感光性ポリイミド前駆体が提案されている（特開昭５９−１６０１４０公報、特開平０５−１５８２３７）。しかしながら通常ポリイミドワニスの場合、極性の高い高沸点溶剤が用いられ、また固形分濃度も高くできないため乾燥時間が長くなり、加工コストが高くなるという問題があった。特開昭６１−１７０７３１公報や特開昭６４−２０３７には、ドライフィルム化した例が記載されているが、それ自体製造が複雑で品質管理が難しく高コストとなってしまう。また３００℃以上の温度をかけないとイミド化が困難かつイミド化したものも伸びの少ない樹脂となってしまうという欠点が指摘されている。また相溶性を有する感光性アクリレートが限定されるため、解像度の向上が難しく特に厚膜に対しては不利と考えられる。
【０００８】
【発明が解決しようとする課題】
本発明の目的は、水酸化ナトリウム水溶液，炭酸ナトリウム水溶液等のアルカリ水溶液で現像できると共に、低エネルギー露光によりファインな画像形成が可能で、現像後の熱処理によるイミド化後の皮膜特性として、優れた耐熱性、導体との接着性、電気特性等を発現するポジ型感光性樹脂組成物、それを用いたドライフィルムを提供することである。
【０００９】
【課題を解決するための手段】
本発明者らは鋭意検討し本発明を完成した。
即ち本発明は
［１］一般式（１）で表される反復単位を含む重合体（Ａ）、酸発生化合物（Ｂ）及び溶剤（Ｃ）を必須成分として含有する感光性樹脂組成物に関する。
【化３】
【化４】
［２］前記［１］の感光性樹脂組成物を、無色透明なフィルムに塗布、乾燥し、フィルム化して得られるドライフィルム。
に関する。
【００１０】
【発明の実施の形態】
以下各成分について詳細に説明する。
［ポリアミド酸アルコキシアルキルエステル］
本発明においてポリアミド酸のアルコキシアルキルエステル、すなわち一般式（１）で表される繰り返し単位を含む重合体は、酸によりアルコキシアルキル基が脱離し、アルカリ水溶液に可溶となる。つまり、ＵＶ露光した部位のアルコキシアルキル基が光により発生した酸の作用によりにカルボキシル基が生じ、アルカリ現像可能となる。すなわちポリアミド酸のアルコキシアルキルエステルを含む本発明の樹脂組成物は、ポジ型感光性樹脂組成物であって現像の後、熱により未露光部のアルコキシアルキル基を脱離させ、カルボン酸を発生させてイミド化が可能であり、ポリイミド膜としての優れた耐熱性、耐薬品性、屈曲性等を発現できる。
【化５】
【化６】
【００１１】
本発明のポリアミド酸アルコキシアルキルエステルは、芳香族ジアミンと芳香族二酸無水物のモル比を変えることにより任意に調製したポリアミド酸に、任意のアルキルビニルエーテルを付加させることにより調製することができる。
【００１２】
芳香族ジアミンとしては特に限定はないが、一般式（３）で表されるジアミンが好ましく使用できる。
【化７】
これらは、単独または２種以上を併用することができる。
【００１３】
芳香族酸二無水物としては特に限定はないが、ピロメリット酸二無水物、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、１，４，５，８−ナフタレンテトラカルボン酸二無水物、１，１−ビス（２，３−ジカルボキシルフェニル）エタン二無水物、２，２−ビス（２，３−ジカルボキシルフェニル）エタン二無水物、２，２−ビス（３，３−ジカルボキシルフェニル）エタン二無水物、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、３，３’４，４’−ビフェニルエーテルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルエーテルテトラカルボン酸二無水物、２，３，５，６−ピリジンテトラカルボン酸二無水物、ピロメリット酸二無水物、３，４，９，１０−ペリレ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、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物等を使用することができる。これらは、単独または２種以上を併用することができる。
【００１４】
また一般式（２）におけるＸは水素原子、ハロゲン原子または炭素数１〜６の直鎖もしくは分岐の無置換アルキル基で、Ｙは水素原子または炭素数１〜６の直鎖もしくは分岐の無置換もしくは置換アルキル基であり、Ｚは炭素数１〜６の直鎖もしくは分岐の無置換もしくは置換アルキル基であって、またはＹとＺは結合して環構造を有していても良い。
【００１５】
Ｘは具体的には水素原子、フッ素原子等のハロゲン原子、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−ブチル基またはｔｅｒｔ−ブチル基等の直鎖もしくは分岐の無置換アルキル基等が挙げられ、Ｙはメチル基、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−ブチル基またはｔｅｒｔ−ブチル基等の直鎖もしくは分岐の無置換アルキル基、ヒドロキシ置換アルキル基、ハロゲン置換アルキル基、シアノ置換アルキル基またはジアルキルアミノ置換アルキル基等が例示でき、Ｚはメチル基、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−ブチル基またはｔｅｒｔ−ブチル基等の直鎖もしくは分岐の無置換アルキル基、ヒドロキシ置換アルキル基、ハロゲン置換アルキル基、シアノ置換アルキル基またはジアルキルアミノ置換アルキル基等が例示できる。
【００１６】
一般式（２）のアルコキシアルキルエステル基の部分であるＸ，Ｃ、Ｏ、ＹおよびＺをまとめて表記するとメトキシメチル基、エトキシメチル基、ｎ−プロポキシメチル基、イソプロポキシメチル基、ｎ−ブトキシメチル基、イソブトキシメチル基、ｓｅｃ−ブトキシメチル基、ｔｅｒｔ−ブトキシメチル基、１−メトキシエチル基、１−エトキシエチル基、１−ｎ−プロポキシエチル基、１−イソプロポキシエチル基、１−ｎ−ブトキシエチル基、１−イソブトキシエチル基、１−ｓｅｃ−ブトキシエチル基、２−エトキシエチル基、２−ｎ−プロポキシエチル基、２−イソプロポキシエチル基、２−ｎ−ブトキシエチル基、２−イソブトキシエチル基、２−ｓｅｃ−ブトキシエチル基、１−メトキシプロピル基、１−エトキシプロピル基、１−ｎ−プロポキシプロピル基、１−イソプロポキシプロピル基、１−ｎ−ブトキシプロピル基、１−イソブトキシプロピル基、１−ｓｅｃ−ブトキシプロピル基、１−ｔｅｒｔ−ブトキシプロピル基、２−メトキシプロピル基、２−エトキシプロピル基、２−ｎ−プロポキシプロピル基、２−イソプロポキシプロピル基、２−ｎ−ブトキシプロピル基、２−イソブトキシプロピル基、２−ｓｅｃ−ブトキシプロピル基、２−ｔｅｒｔ−ブトキシプロピル基、３−メトキシプロピル基、３−エトキシプロピル基、３−ｎ−プロポキシプロピル基、３−イソプロポキシプロピル基、３−ｎブトキシプロピル基、３−イソブトキシプロピル基、３−ｓｅｃ−ブトキシプロピル基、３−ｔｅｒｔ−ブトキシプロピル基等の無置換アルキル基、１−メトキシ−１−ヒドロキシメチル基、１−（１−ヒドロキシ）メトキシメチル基、１−（１−ヒドロキシ）メトキシエチル基等のヒドロキシ置換アルコキシアルキル基、トリフルオロメトキシメチル基、１−メトキシ−２，２，２−トリフルオロエチル基、１−トリフルオロメトキシ−２，２，２―トリフルオロエチル基等のハロゲン置換アルコキシアルキル基、１−メトキシ−１−シアノメチル基、１−（１−シアノ）メトキシメチル基、１−（１−シアノ）メトキシエチル基等のシアノ置換アルコキシアルキル基、１，１−ジメチルアミノメトキシメチル基等のジアルキルアミノ置換アルコキシアルキル基、テトラヒドロフラン−２−イルオキシ基、テトラヒドロピラン−２−イルオキシ基等の無置換環状エーテル、２−メチルテトラヒドロフラン−２−イルオキシ基、２−メチルテトラヒドロピラン−２−イルオキシ基等のアルキル置換環状エーテル、または、２−フルオロテトラヒドロフラン−２−イルオキシ基、２−フルオロテトラヒドロフラン−２−イルオキシ基等のハロゲン置換環状エーテル等が例示できる。
【００１７】
好ましくは、一般式（２）においてＸが水素原子、フッ素原子または炭素数１〜３の直鎖もしくは分岐の無置換アルキル基で、Ｙが水素原子または炭素数１〜３の直鎖もしくは分岐の無置換もしくは置換アルキル基であり、Ｚが炭素数１〜３の直鎖または分岐の無置換もしくは置換アルキル基またはＹとＺが結合して形成された環構造が炭素数３〜６の無置換もしくは置換環状エーテルである。具体的には一般式（２）のＸ，Ｃ、Ｏ、ＹおよびＺをまとめて表記するとメトキシメチル基、エトキシメチル基、ｎ−プロポキシメチル基、イソプロポキシメチル基、１−メトキシエチル基、１−エトキシエチル基、１−ｎ−プロポキシエチル基、１−イソプロポキシエチル基、２−エトキシエチル基、２−ｎ−プロポキシエチル基、２−イソプロポキシエチル基、１−メトキシプロピル基、１−エトキシプロピル基、１−メトキシ−１−ヒドロキシメチル基、１−（１−ヒドロキシ）メトキシメチル基、１−（１−ヒドロキシ）メトキシエチル基、トリフルオロメトキシメチル基、１−メトキシ−２，２，２−トリフルオロエチル基、１−トリフルオロメトキシ−２，２，２−トリフルオロエチル基、テトラヒドロフラン−２−イルオキシ基、テトラヒドロピラン−２−イルオキシ基、２−メチルテトラヒドロフラン−２−イルオキシ基、２−メチルテトラヒドロピラン−２−イルオキシ基または２−フルオロテトラヒドロフラン−２−イルオキシ基等が例示できる。
＜アルコキシアルキルエステル化方法＞
ポリアミド酸のアルコキシアルキルエステルは通常以下の方法で合成される。
５〜７０質量％、好ましくは１５〜５０質量％のポリアミド酸溶液を−１５〜１００℃、好ましくは０〜６０℃に保持し、攪拌しながら酸触媒を１０〜１０００ｐｐｍ、好ましくは５０〜５００ｐｐｍ加える。この時の酸触媒としては、塩酸、蓚酸、ｐ−トルエンスルホン酸が好ましい。次にアルキルビニルエーテルを１〜３００分、好ましくは１０〜６０分かけて加える。ポリアミド酸濃度を上記範囲に保持することにより、攪拌を十分に行うことができ、反応速度制御が容易となる。また反応温度を上記範囲に保持することにより、発熱によるモノマーのゲル化や異種反応を起こすことなく目的とするアルコキシエステルを得ることができる。この時、アルキルビニルエーテルのカルボキシル基に対するモル比は１．０〜３．０倍、好ましくは１．１〜２．０倍とする。モル比を制御することにより、アルコキシアルキルエステルの貯蔵安定性及び光反応性をを制御できる。反応終了後、重炭酸ソーダを溶かした飽和食塩水を加え水洗する。この時の重炭酸ソーダの量は、酸触媒の２倍モルが目安である。ｐＨが７．０〜７．５であることを確認後分液する。有機相に１５％燐酸１ソーダ水溶液を加え水洗する。ｐＨが６．５〜７．０であることを確認後分液する。エステル化率は、ポリアミド酸骨格及びアルキルビニルエーテル骨格により異なるが、通常全カルボン酸の６５〜１００モル％の範囲にあり、残存モノマーは留去する。
【００１８】
ポリアミド酸アルコキシアルキルエステルの含有量は、組成物中５〜７０質量％（固形分換算）、好ましくは１５〜５０質量％である。含有量が５質量％以上含有することにより、アルカリ溶液による溶解性が向上し、高い解像度を得ることができると同時に、最終硬化膜としてポリイミドの特長である耐熱性、耐薬品性、電気絶縁性等を発現できる。また７０質量％以下にし、光酸発生剤を併用することでポジ型感光性樹脂とできる。
【００１９】
本発明は、必要に応じて多官能アクリレート、エポキシ樹脂、フェノール樹脂及びイソシアネートを併用することができる。
【００２０】
［光酸発生剤］
本発明に用いる光酸発生剤は、トリアジン系、オニウム塩系、ジフェニルヨードニウム系、ジアゾジスルホン系、トリフェニルスルホニウム系等、α、α−ジクロロ−４−フェノキシアセトフェノン及び４，４‘−（α、α―ジクロロアセチル）ジフェニルエーテル等何れでも使用することができる。これらは、特性低下を招かない限り、２種以上を併用しても差し支えない。
【００２１】
光酸発生剤の添加量は、所望のエネルギーで硬化できる量であれば限定はないが、通常組成物中（固形分換算）に０．０５〜２０．０質量％、好ましくは０．１〜１０．０質量％、更に好ましくは０．２〜５．０質量％である。０．０５質量％よりも多くいれることにより、アルコキシアルキルエステルの脱離が現像時のコントラストを満足できるに十分な量となる。また２０．０質量％以下とすることで、最終塗膜の耐マイグレーション性の保持性が向上する。
【００２２】
［溶 剤］
本発明に用いる溶剤は、樹脂組成物の一部または全部を溶解し易いことが好ましいが、作業性（乾燥性含む）、樹脂物性を向上させるかまたは損なわない範囲で貧溶媒を使用することができる。
【００２３】
具体的な溶剤としては例えばケトン類、アルコール類、エーテル及びエステル類、エステル類、グリコールエーテル類、アミン、アミド類、炭化水素類等が挙げられる。これらは単独で用いても良いが、複数を併用しても良い。例えば、低沸点溶剤と高沸点溶剤を混合することにより乾燥時の発泡を抑制することができ、ドライフィルムの品質を向上させることができる。
【００２４】
本発明において、ワニスを調製する場合、作業性（乾燥性含む）、樹脂物性を向上させるかまたは損なわない範囲であれば特に量は規定されないが、好ましくは樹脂組成物中３０〜９０重量％、更に好ましくは４５〜７０重量％を使用すると、ドライフィルム作製時レベリング性が向上し、品質の向上につながる。
【００２５】
ケトン類では例えばアセトン，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、シクロペンタノン、メチル−ｎ−アミルケトン、アセトニルアセトン、イソホロン、アセトフェノン等が挙げられ、これら単独または複数を併用できる。
【００２６】
エーテル及びアセタール類では例えばｎ−ブチルエーテル、ｎ−ヘキシルエーテル、エチルフェニルエーテル、１，４−ジオキサン、トリオキサン、ジエチルアセタール、１，２−ジオキソラン、テトラヒドロピラン、テトラヒドロフラン、等が挙げられ、これら単独または複数を併用できる。
【００２７】
アルコール類では例えばエチルアルコール、イソプロピルアルコール、ｎ−ブタノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ヘキシレングリコール、テキサノール、等が挙げられ、これら単独または複数を併用できる。
【００２８】
エステル類では例えばギ酸メチル、ギ酸エチル、ギ酸プロピル、ギ酸イソブチル、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ｎ−ブチル、酢酸ベンジル、酢酸イソアミル、乳酸エチル、安息香酸メチル、シュウ酸ジエチル、コハク酸ジメチル、グルタミン酸ジメチル、アジピン酸ジメチル、炭酸メチル、炭酸エチル、炭酸プロピル、炭酸ブチル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルアセテート、エチレングリコールモノプロピルアセテート、エチレングリコールモノブチルエーテルアセテート、エチレングリコールジアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、プロピレングリコールジアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールジアセテート、等が挙げられ、これら単独または複数を併用できる。
【００２９】
グルコールエーテル類では例えばエチレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールジブチルエーテル等が挙げられ、これら単独または複数を併用できる。
【００３０】
アミン、アミド類では例えばジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ピリジン、ピラジン、等が挙げられ、これら単独または複数を併用できる。
【００３１】
炭化水素類では例えばｎ−ヘプタン、ｎ−オクタン、ｎ−デカン、シクロヘキサン、ベンゼン、トルエン、キシレン、エチルベンゼン、ジエチルベンゼン、ピネン等が挙げられ、これら単独または複数を併用できる。
その他、ジメチルスルホキシド等も使用することができる。
これらは作業性（乾燥性含む）、樹脂物性を向上させるかまたは損なわない範囲であれば同一の群以外と併用しても差し支えない。
【００３２】
本発明において、固形分１０〜９０質量％に調整された該感光性樹脂組成物を、一定厚みの無色透明なフィルムに一定厚みで塗布、乾燥し、感光性ポリイミドフィルムを得ることができる。
【００３３】
ここで無色透明なフィルムとしては、低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、ポリエステル、ポリカーボネート、ポリアリレート、エチレン／シクロデセン共重合体（三井化学製、商品名（商標）：ＡＰＥＬ）等を用いる。ポリアミド酸は水分により物性が変化するため、低透湿性の樹脂が望ましく、従ってこれらの中では、ＡＰＥＬ（商標）及びポリエチレン、ポリプロピレンが好適である。また、塗工性、付着性、ロール性、強靱性、コスト等を考慮した時、フィルムの厚みが１５〜１００μｍ、好ましくは３０〜７５μｍであるポリエチレン、ポリプロピレン、エチレン含有率の高いＡＰＥＬ（商標）が更に好ましい。
【００３４】
感光性ポリイミドフィルムは、上記のフィルムにリバースロールコーターやグラビアロールコーター、コンマコーター、カーテンコーター等の公知の方法で塗布することができる。乾燥は、熱風乾燥や遠赤外線、近赤外線を用いた乾燥機で、温度５０〜１２０℃で乾燥でき、より好ましくは６０〜１００℃で１０〜６０分乾燥することにより得ることができる。
【００３５】
感光性ポリイミドフィルムの膜厚は、５〜１００μｍ、より好ましくは１０〜５０μｍである。膜厚が５μｍ以上は絶縁信頼性に問題が無く、１００μｍ以下にすることで解像度を向上させることができる。
感光性皮膜は、微細孔や微細幅ラインを形成するため、任意のパターンが書かれたフォトマスクを通して露光される。露光量は、樹脂組成物により異なるが、通常３０〜１０００ｍｊ／ｃｍ２であり、より低エネルギーで解像度の高いことが要求される。この時使用される活性光線としては、例えば電子線、紫外線、Ｘ線等が挙げられるが、好ましくは紫外線が良い。光源としては低圧水銀灯、高圧水銀灯、超高圧水銀灯、ハロゲンランプ等を使用することができる。このようにして得られた皮膜は、銅箔のエッチングに用いられる塩化第二銅、塩化第二鉄等の酸性のエッチング液に対する耐性に優れている。
【００３６】
次に現像液を用い、浸漬法やスプレー法にて現像を行う。現像液としては、水酸化ナトリウム水溶液、炭酸ナトリウム水溶液等のアルカリ水溶液が使用できる。
このようにして、レジスト膜により所定のパターンが形成された銅張り積層板は次に上記のようなエッチング液を用い、レジスト膜の無い部分の銅箔を溶解・除去し、所定の回路パターンを形成できる。回路パターン形成後は、水酸化ナトリウム等のアルカリ溶液で除去される。
【００３７】
【実施例】
以下、代表的な実施例により本発明を詳細に説明するがこれに限定されたものではない。
（合成例１）
〔ポリアミド酸アルコキシアルキルエステルＰＡＥ１〕
反応器（攪拌機、還流冷却器及び窒素導入管付き）中、窒素雰囲気下、Ｎ，Ｎ−ジメチルアセトアミド３５０ｇ、ジエチレングリコールジメチルエーテル２９１ｇに１，３−ビス（３−アミノフェノキシ）ベンゼン１７３．２ｇ（０．５９３モル）を溶解し、これを攪拌しながらピロメリット酸二無水物１２６．８ｇ（０．５８２モル）（モル比０．９８１）を乾燥固体のまま少量づつ添加した。この間反応温度を２５〜３０℃に保ち、添加後１０時間窒素雰囲気下で攪拌を継続した。次に液温を５０〜６０℃に昇温し、その中にイソブチルビニルエーテル５９．０ｇ（０．５９０モル）を約３０分かけて添加した。反応を更に２０時間行い固形分３５質量％のポリアミド酸イソブトキシエチルエステル溶液（ＰＡＥ１）を得た。
（合成例２）
〔ポリアミド酸アルコキシアルキルエステルＰＡＥ２〕
合成例１の１，３−ビス（３−アミノフェノキシ）ベンゼンの代わりに、１，３−ビス（３−アミノフェノキシ）ビフェニルを用い、合成例１と同一モル比（０．９８１）、反応条件で行った。更にイソブチルビニルエーテルの代わりにｔ−ブチルビニルエーテル５９．０ｇ（０．５９０モル）を反応させ、固形分３５質量％のポリアミド酸ｔ−ブトキシエチルエステル溶液（ＰＡＥ２）を得た。
【００３８】
（実施例１）
合成例１で得られたＰＡＥ１を２００質量部と光酸発生剤ジフェニル−４−メチルフェニルスルフォニウムトリフルオロメタンスルフォネート（Ｗａｋｏ社製、以下ＷＰＡＧ−３３６と記す）１．５質量部を混合溶解し、ワニスを調製した。このワニスを幅３０ｃｍ、厚さ２０μｍのキャリアフィルムとしてポリプロピレンフィルム上に約１００μｍの厚みで塗工後、熱風循環乾燥炉内で８０℃×２０分間乾燥、厚さ２０μｍのリリースフィルムを張り合わせドライフィルムを作製した。作製したドライフィルムは、リリースフィルムを剥がした後、パターン形成されたサスペンション基材（ＳＵＳ／ＰＩ／Ｃｕ＝２０／１０／１２μｍ）銅箔面上に重ね合わせ、位置合わせ後真空ラミネート装置で１００℃×２０秒圧着した。次に露光量１００ｍｊ／ｃｍ２で照射、キャリアフィルムを剥がした後、３０±１℃に保持された１％Ｎａ２ＣＯ３を０．１５ＭＰａで噴霧後、２５０℃×１０分間加熱硬化させ評価用テストピースに供した。
【００３９】
（実施例２）
合成例２で得られたＰＡＥ２を２００質量部と光酸発生剤 ビス（シクロヘキシルスルフォニル）ジアゾメタン（Ｗａｋｏ社製、以下ＷＰＡＧ−１４５と記す）２．５質量部を混合溶解し、ワニスを調製した。このワニスを幅３０ｃｍ、厚さ２０μｍのキャリアフィルムとしてポリプロピレンフィルム上に約１００μｍの厚みで塗工後、熱風循環乾燥炉内で８０℃×２０分間乾燥、厚さ２０μｍのカバーフィルムを張り合わせドライフィルムを作製した。作製したドライフィルムは、カバーフィルムを剥がした後、パターン形成されたサスペンション基材（ＳＵＳ／ＰＩ／Ｃｕ＝２０／１０／１２μｍ）銅箔面上に重ね合わせ、位置合わせ後真空ラミネート装置で１００℃×２０秒圧着した。次に露光量１００ｍｊ／ｃｍ２で照射、キャリアフィルムを剥がした後、３０±１℃に保持された１％Ｎａ２ＣＯ３を０．１５ＭＰａで噴霧後、２５０℃×１０分間加熱硬化させ評価用テストピースに供した。
（実施例３）
合成例１で得られたＰＡＥ１を２００質量部と光酸発生剤ジフェニル−４−メチルフェニルスルフォニウムトリフルオロメタンスルフォネート（Ｗａｋｏ社製、以下ＷＰＡＧ−３３６と記す）１．５質量部およびビスフェノールＡ型エポキシ樹脂Ｒ１３９Ｓ（商品名：三井化学（株）社製、ＥＥＷ＝１８４ｇ／ｅｑ）１８．０質量部、フェノールノボラック樹脂ＰＳＭ−４３２６（群栄化学工業社製、ＯＨ当量＝１０４ｇ／ｅｑ）１０．０質量部を混合溶解し、ワニスを調製した。このワニスを幅３０ｃｍ、厚さ２０μｍのキャリアフィルムとしてポリプレピレンフィルム上に約１００μｍの厚みで塗工後、熱風循環乾燥炉内で８０℃×２０分間乾燥、厚さ２０μｍのカバーフィルムを張り合わせドライフィルムを作製した。作製したドライフィルムは、カバーフィルムを剥がした後、パターン形成されたサスペンション基材（ＳＵＳ／ＰＩ／Ｃｕ＝２０／１０／１２μｍ）銅箔面上に重ね合わせ、位置合わせ後真空ラミネート装置で１００℃×２０秒圧着した。次に露光量１００ｍｊ／ｃｍ２で照射、キャリアフィルムを剥がした後、３０±１℃に保持された１％Ｎａ２ＣＯ３を０．１５ＭＰａで噴霧後、２５０℃×１０分間加熱硬化させ評価用テストピースに供した。
【００４０】
（比較例１）
反応器（攪拌機、還流冷却器及び窒素導入管付き）中、窒素雰囲気下、Ｎ，Ｎ−ジメチルアセトアミド３５０ｇ、ジエチレングリコールジメチルエーテル３５０ｇに１，３−ビス（３−アミノフェノキシ）ベンゼン１７３．２ｇ（０．５９３モル）を溶解し、これを攪拌しながらピロメリット酸二無水物１２６．８ｇ（０．５８２モル）（モル比０．９８１）を乾燥固体のまま少量づつ添加した。この間反応温度を２５〜３０℃に保ち、添加後２０時間窒素雰囲気下で攪拌を継続し、固形分３０質量％のポリアミック酸溶液（ＰＡ１）を得た。このワニスを幅３０ｃｍ、厚さ２０μｍのキャリアフィルムとしてポリプレピレンフィルム上に約１００μｍの厚みで塗工後、熱風循環乾燥炉内で８０℃×２０分間乾燥、厚さ２０μｍのカバーフィルムを張り合わせドライフィルムを作製した。作製したドライフィルムは、カバーフィルムを剥がした後、パターン形成されたサスペンション基材（ＳＵＳ／ＰＩ／Ｃｕ＝２０／１０／１２μｍ）銅箔面上に重ね合わせ、位置合わせ後真空ラミネート装置で１００℃×２０秒圧着し、２５０℃×１０分間加熱硬化させ評価用テストピースに供した。
（比較例２）
３，４’−ジアミノフェニルエーテル６０１ｇ、無水ピロメリット酸（酸価：１０１１ｍｇＫＯＨ／ｇ）４３６ｇ、γ−ブチロラクトン１０３０ｇを４０℃×５Ｈｒｓ反応させ、末端アミンカルボキシル基含有ポリアミドプレポリマー（固形分の酸価：２１２．５ｍｇＫＯＨ／ｇ）を得た。次にグリシジルメタクリレート５０８ｇ及びｐ−メトキシフェノール１．７５ｇをし込み、９５℃×１０Ｈｒｓ反応し、固形分６０質量％のカルボキシル基含有ポリアミドオリゴマー（ＰＯ−１）を得た。このＰＯ−１を１５０ｇとジペンタエリスリトールε−カプロラクトン付加物のポリアクリレート（商品名：ＤＰＣＡ−６０、日本化薬社製）２０ｇ及び光開始剤としてベンゾフェノン５．０ｇ、ＤＥＴＸ２．０ｇを混合し、感光性樹脂組成物を得た。このワニスを幅３０ｃｍ、厚さ２０μｍのキャリアフィルムとしてポリプレピレンフィルム上に約１００μｍの厚みで塗工後、熱風循環乾燥炉内で８０℃×２０分間乾燥、厚さ２０μｍのカバーフィルムを張り合わせドライフィルムを作製した。作製したドライフィルムは、カバーフィルムを剥がした後、パターン形成されたサスペンション基材（ＳＵＳ／ＰＩ／Ｃｕ＝２０／１０／１２μｍ）銅箔面上に重ね合わせ、位置合わせ後真空ラミネート装置で１００℃×２０秒圧着した。次に露光量１００ｍｊ／ｃｍ２で照射、キャリアフィルムを剥がした後、３０±１℃に保持された１％Ｎａ２ＣＯ３を０．１５ＭＰａで噴霧後、２５０℃×１０分間加熱硬化させ評価用テストピースに供した。
【００４１】
上記実施例、比較例で作製されたドライフィルム及び評価用テストピースを用い、以下の項目につき評価を行った。
評価１ 解像度：３００ｍｊ／ｃｍ２で露光し、３０±１℃の１．０％Ｎａ２ＣＯ３ａｑを０．１５Ｐａの圧力で噴霧、現像、硬化（２５０℃×１０分）後の解像度がヴィアホール１００μｍφ以下で有るか否かを確認した。
評価２ クロスカットピール：ＪＩＳ Ｋ ５４０４に準じた。
評価３ はんだ耐熱性：±５℃に保持された溶融はんだに樹脂面を下にして２０秒フロートした。（ＪＰＣＡ−ＢＭ０２に準拠）温度を１０℃刻みで上げ、皮膜の膨れ等が発生した時の温度−１０℃を測定値とした。
評価４ Ｔｇ：厚み３０〜３５μｍ、幅４ｍｍ、長さ２５ｍｍの硬化フィルムを作製し、セイコー電子社製ＴＭＡ／ＳＳ１００を用い、引張りモード加重５ｇ、昇温速度２℃／Ｍｉｎ．で測定した。
実施例１〜３及び比較例１〜２の評価結果を表１に示す。
【００４２】
【評価結果】
【表１】
【発明の効果】
本発明の樹脂組成物は水酸化ナトリウム水溶液，炭酸ナトリウム水溶液等のアルカリ水溶液で現像できると共に、低エネルギー露光によりファインな画像形成が可能で、現像後の熱処理後の皮膜特性として、ポリイミド特有の優れた耐熱性、導体との接着性、電気特性等を発現できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a photosensitive resin composition containing an alkoxyalkyl ester of polyamic acid as a main component, and more particularly to a dry film using the photosensitive resin composition.
[0002]
[Prior art]
In the recent “multimedia” society, with the rapid increase in the amount of information on a global scale, the exchange and transmission of information data is required to have a large capacity, high speed, and digitization. In response to these demands, electronic information systems and devices are becoming more highly integrated and faster, and electronic information equipment is becoming more sophisticated and functional (composite and integrated) and more portable (higher density). It is getting intense.
[0003]
The importance of the “mounting technology” serving as an interface between these electronic information devices and semiconductor devices has been increasingly recognized in the world for higher density. Along with the semiconductor device that plays a leading role in this “mounting technology”, a semiconductor package has been attracting attention today, and the establishment of related technology is urgently required.
[0004]
Recently, the fineness of the conductor circuit pattern and the improvement of the positional accuracy, the miniaturization of the mounted components, and the fine pitch of the leads of the IC package have improved the image accuracy and the positional accuracy of the formation of an insulating film such as an interlayer insulating film and a solder resist film. Have been required. Therefore, in recent years, a method of forming an interlayer insulating film solder resist film or an insulating film by using the photo method has been widely adopted as a method for forming a film with high accuracy.
[0005]
In the photo method, a photosensitive resin composition is applied to a substrate to a desired thickness and then dried to form a photosensitive film. A negative photomask is placed on the photosensitive film, and the photosensitive film is exposed to actinic rays such as ultraviolet rays. It is common to perform exposure printing. The photosensitive film is hardened by actinic light transmitted through the transparent portion of the photomask, and the unexposed portion is removed by a developer. The photosensitive film formed by the photo method is further cured by heat or actinic rays, and becomes a solder resist film or an insulating film. Since the formed image can be formed with an accuracy very close to that of a photomask, a fine image and positional accuracy can be easily obtained.
[0006]
However, this method requires the steps of coating on the surface of the base material and drying the solvent as described above, which complicates the manufacturing process of the FPC, and has a difficulty in reducing the defect rate due to pinholes and foreign matter. there were. Therefore, researches on negative-type interlayer insulating films and photo-solder resist films developed with an aqueous alkali solution have been actively conducted in recent years. For example, Japanese Patent Publication No. Sho 56-40329 discloses that an unsaturated monocarboxylic acid is added to an epoxy resin to form a polybasic acid anhydride. A photosensitive resin composition using a reaction product obtained by adding a product as a base polymer is disclosed. JP-A-61-243869 discloses a photo solder resist composition in which a reaction product obtained by adding a polybasic acid anhydride to a novolak type epoxy acrylate or the like is used as a base polymer and an aqueous alkali solution is used as a developer. . However, the solder resist film obtained with the above composition is insufficient in heat resistance, solvent resistance and chemical resistance, and cannot be said to have sufficient insulation and dielectric properties. In addition, since it is a negative type, it is difficult to improve chemical resistance, it is difficult to form a fine circuit, and it has not been possible to apply it to a thin BGA or the like.
[0007]
On the other hand, polyimide obtained by heat-treating a polyamic acid as a polyimide precursor has been used as an IC protective film and an interlayer insulating film because of its excellent heat resistance, chemical resistance, dielectric properties, etc. A photosensitive polyimide precursor capable of forming a pattern directly by development has been proposed (JP-A-59-160140, JP-A-05-158237). However, a polyimide varnish usually has a problem that a high-polarity high-boiling solvent is used and the solid content cannot be increased, so that the drying time becomes longer and the processing cost becomes higher. JP-A-61-170731 and JP-A-64-2037 describe examples in which a dry film is formed, but the production itself is complicated, quality control is difficult, and the cost is high. In addition, it is pointed out that imidization is difficult unless imposed at a temperature of 300 ° C. or more, and the imidized resin also becomes a resin with little elongation. In addition, since the photosensitive acrylate having compatibility is limited, it is difficult to improve the resolution, and it is considered to be disadvantageous particularly for a thick film.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to develop with an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous sodium carbonate solution, to form a fine image by low energy exposure, and to obtain an excellent film property after imidization by heat treatment after development. An object of the present invention is to provide a positive photosensitive resin composition exhibiting heat resistance, adhesion to a conductor, electrical characteristics, and the like, and a dry film using the same.
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies and completed the present invention.
That is, the present invention
[1] A photosensitive resin composition containing, as essential components, a polymer (A) containing a repeating unit represented by the general formula (1), an acid generating compound (B), and a solvent (C).
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[2] A dry film obtained by applying the photosensitive resin composition of the above [1] to a colorless and transparent film, drying and forming a film.
About.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, each component will be described in detail.
[Polyamic acid alkoxyalkyl ester]
In the present invention, an alkoxyalkyl ester of a polyamic acid, that is, a polymer containing a repeating unit represented by the general formula (1), has an alkoxyalkyl group eliminated by an acid and becomes soluble in an aqueous alkaline solution. In other words, the carboxyl group is generated by the action of the acid generated by the light in the alkoxyalkyl group at the site exposed to UV light, and alkali development can be performed. That is, the resin composition of the present invention containing an alkoxyalkyl ester of polyamic acid is a positive-type photosensitive resin composition, and after development, the alkoxyalkyl group in the unexposed portion is removed by heat to generate a carboxylic acid. And can exhibit excellent heat resistance, chemical resistance, flexibility and the like as a polyimide film.
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[0011]
The alkoxyalkyl polyamic acid ester of the present invention can be prepared by adding an arbitrary alkyl vinyl ether to a polyamic acid arbitrarily prepared by changing a molar ratio of an aromatic diamine and an aromatic dianhydride.
[0012]
The aromatic diamine is not particularly limited, but a diamine represented by the general formula (3) can be preferably used.
Embedded image
These can be used alone or in combination of two or more.
[0013]
Although there is no particular limitation on the aromatic dianhydride, pyromellitic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxylphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyl Phenyl) ethane dianhydride, 2,2-bis (3,3-dicarboxyphenyl) ethane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3,3′4,4′-biphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyl ether tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride Anhydride, Piromeri Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Benzophenonetetracarboxylic dianhydride or the like can be used. These can be used alone or in combination of two or more.
[0014]
In the general formula (2), X is a hydrogen atom, a halogen atom or a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, and Y is a hydrogen atom or a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms. Or, it is a substituted alkyl group, Z is a linear or branched unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, or Y and Z may be bonded to each other to have a ring structure.
[0015]
X is specifically a hydrogen atom, a fluorine atom or the like, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group. A chain or branched unsubstituted alkyl group; and Y is a linear group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group. Or a branched unsubstituted alkyl group, a hydroxy-substituted alkyl group, a halogen-substituted alkyl group, a cyano-substituted alkyl group or a dialkylamino-substituted alkyl group; and Z is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Straight-chain or branched unsubstituted alkyl such as -butyl, isobutyl, sec-butyl or tert-butyl; Group, hydroxy-substituted alkyl group, halogen-substituted alkyl group, a cyano-substituted alkyl group or dialkyl amino-substituted alkyl group can be exemplified.
[0016]
X, C, O, Y and Z, which are parts of the alkoxyalkyl ester group of the general formula (2), are collectively described as a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, an n-butoxy group. Methyl group, isobutoxymethyl group, sec-butoxymethyl group, tert-butoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n -Butoxyethyl group, 1-isobutoxyethyl group, 1-sec-butoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2 -Isobutoxyethyl group, 2-sec-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group 1-n-propoxypropyl group, 1-isopropoxypropyl group, 1-n-butoxypropyl group, 1-isobutoxypropyl group, 1-sec-butoxypropyl group, 1-tert-butoxypropyl group, 2-methoxypropyl Group, 2-ethoxypropyl group, 2-n-propoxypropyl group, 2-isopropoxypropyl group, 2-n-butoxypropyl group, 2-isobutoxypropyl group, 2-sec-butoxypropyl group, 2-tert- Butoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propoxypropyl, 3-isopropoxypropyl, 3-nbutoxypropyl, 3-isobutoxypropyl, 3-sec-butoxy An unsubstituted alkyl group such as a propyl group, a 3-tert-butoxypropyl group, Hydroxy-substituted alkoxyalkyl groups such as a toxic-1-hydroxymethyl group, a 1- (1-hydroxy) methoxymethyl group, a 1- (1-hydroxy) methoxyethyl group, a trifluoromethoxymethyl group, and a 1-methoxy-2,2 Halogen-substituted alkoxyalkyl groups such as 1,2-trifluoroethyl group, 1-trifluoromethoxy-2,2,2-trifluoroethyl group, 1-methoxy-1-cyanomethyl group, 1- (1-cyano) methoxymethyl Group, cyano-substituted alkoxyalkyl group such as 1- (1-cyano) methoxyethyl group, dialkylamino-substituted alkoxyalkyl group such as 1,1-dimethylaminomethoxymethyl group, tetrahydrofuran-2-yloxy group, tetrahydropyran-2- Unsubstituted cyclic ethers such as yloxy group, 2-methyltetrahydride Alkyl-substituted cyclic ethers such as a lofuran-2-yloxy group and 2-methyltetrahydropyran-2-yloxy group, or halogen-substituted cyclic ethers such as a 2-fluorotetrahydrofuran-2-yloxy group and a 2-fluorotetrahydrofuran-2-yloxy group Ether and the like can be exemplified.
[0017]
Preferably, in the general formula (2), X is a hydrogen atom, a fluorine atom or a straight-chain or branched unsubstituted alkyl group having 1 to 3 carbon atoms, and Y is a hydrogen atom or a straight-chain or branched alkyl group having 1 to 3 carbon atoms. An unsubstituted or substituted alkyl group, wherein Z is a straight-chain or branched unsubstituted or substituted alkyl group having 1 to 3 carbon atoms or a ring structure formed by combining Y and Z is 3 to 6 carbon atoms; Alternatively, it is a substituted cyclic ether. Specifically, when X, C, O, Y and Z in the general formula (2) are collectively described, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, a 1-methoxyethyl group, -Ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 1-methoxypropyl group, 1-ethoxy Propyl group, 1-methoxy-1-hydroxymethyl group, 1- (1-hydroxy) methoxymethyl group, 1- (1-hydroxy) methoxyethyl group, trifluoromethoxymethyl group, 1-methoxy-2,2,2 -Trifluoroethyl group, 1-trifluoromethoxy-2,2,2-trifluoroethyl group, tetrahydrofuran-2-yloxy , Tetrahydropyran-2-yloxy group, 2-methyl-tetrahydrofuran-2-yloxy group, 2-methyl-tetrahydropyran-2-yloxy group or a 2-fluoro-tetrahydrofuran-2-yloxy group and the like.
<Alkoxyalkyl esterification method>
The alkoxyalkyl ester of polyamic acid is usually synthesized by the following method.
The polyamic acid solution of 5 to 70% by mass, preferably 15 to 50% by mass is maintained at -15 to 100 ° C, preferably 0 to 60 ° C, and the acid catalyst is added with stirring at 10 to 1000 ppm, preferably 50 to 500 ppm. . As the acid catalyst at this time, hydrochloric acid, oxalic acid, and p-toluenesulfonic acid are preferable. The alkyl vinyl ether is then added over 1 to 300 minutes, preferably 10 to 60 minutes. By keeping the polyamic acid concentration in the above range, stirring can be sufficiently performed, and the reaction rate control becomes easy. By maintaining the reaction temperature in the above range, the desired alkoxyester can be obtained without causing gelation of the monomer due to heat generation or heterogeneous reaction. At this time, the molar ratio of the alkyl vinyl ether to the carboxyl group is 1.0 to 3.0 times, preferably 1.1 to 2.0 times. By controlling the molar ratio, the storage stability and photoreactivity of the alkoxyalkyl ester can be controlled. After the completion of the reaction, a saturated saline solution in which sodium bicarbonate is dissolved is added and washed with water. At this time, the amount of sodium bicarbonate is about twice as much as the acid catalyst. After confirming that the pH is 7.0 to 7.5, the mixture is separated. A 15% aqueous solution of 1% sodium phosphate is added to the organic phase and washed with water. After confirming that the pH is 6.5 to 7.0, liquid separation is performed. The esterification rate varies depending on the polyamic acid skeleton and the alkyl vinyl ether skeleton, but is usually in the range of 65 to 100 mol% of the total carboxylic acid, and the remaining monomer is distilled off.
[0018]
The content of the polyamide acid alkoxyalkyl ester is 5 to 70% by mass (in terms of solid content) in the composition, and preferably 15 to 50% by mass. When the content is 5% by mass or more, solubility in an alkaline solution is improved, and high resolution can be obtained. At the same time, heat resistance, chemical resistance, and electrical insulation characteristics of polyimide as a final cured film are obtained. Etc. can be expressed. When the content is 70% by mass or less and a photoacid generator is used in combination, a positive photosensitive resin can be obtained.
[0019]
In the present invention, a polyfunctional acrylate, an epoxy resin, a phenol resin and an isocyanate can be used in combination as needed.
[0020]
[Photoacid generator]
The photoacid generator used in the present invention includes triazine-based, onium salt-based, diphenyliodonium-based, diazodisulfone-based, triphenylsulfonium-based, and the like, α, α-dichloro-4-phenoxyacetophenone and 4,4 ′-(α, Any of α-dichloroacetyl) diphenyl ether and the like can be used. These may be used in combination of two or more as long as the characteristics are not deteriorated.
[0021]
The amount of the photoacid generator to be added is not limited as long as it can be cured with desired energy, but is usually 0.05 to 20.0% by mass, preferably 0.1 to 2% by mass in the composition (in terms of solid content). It is 10.0% by mass, more preferably 0.2 to 5.0% by mass. By adding more than 0.05% by mass, the elimination of the alkoxyalkyl ester becomes an amount sufficient to satisfy the contrast during development. When the content is 20.0% by mass or less, retention of migration resistance of the final coating film is improved.
[0022]
[Solvent]
The solvent used in the present invention preferably dissolves a part or all of the resin composition easily, but it is preferable to use a poor solvent as long as the workability (including dryness) and the resin properties are improved or not impaired. it can.
[0023]
Specific solvents include, for example, ketones, alcohols, ethers and esters, esters, glycol ethers, amines, amides, hydrocarbons and the like. These may be used alone or in combination. For example, foaming during drying can be suppressed by mixing a low-boiling solvent and a high-boiling solvent, and the quality of a dry film can be improved.
[0024]
In the present invention, when preparing a varnish, the amount is not particularly limited as long as it is within a range that does not impair or impair workability (including dryness) and resin properties, but is preferably 30 to 90% by weight in the resin composition, More preferably, when it is used in an amount of 45 to 70% by weight, the leveling property at the time of producing a dry film is improved, which leads to an improvement in quality.
[0025]
Ketones include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl-n-amyl ketone, acetonylacetone, isophorone, acetophenone and the like, and these can be used alone or in combination.
[0026]
Examples of ethers and acetals include n-butyl ether, n-hexyl ether, ethyl phenyl ether, 1,4-dioxane, trioxane, diethyl acetal, 1,2-dioxolane, tetrahydropyran, tetrahydrofuran, and the like. Can be used together.
[0027]
Examples of alcohols include ethyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, hexylene glycol, texanol, and the like, and these can be used alone or in combination.
[0028]
Esters include, for example, methyl formate, ethyl formate, propyl formate, isobutyl formate, methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, benzyl acetate, isoamyl acetate, ethyl lactate, methyl benzoate, diethyl oxalate, dimethyl succinate , Dimethyl glutamate, dimethyl adipate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, ethylene glycol monopropyl acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Tate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate, etc., and can be used in combination of these single or multiple.
[0029]
In the glycol ethers, for example, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether Propylene glycol diethyl ether, propylene glycol monobutyl ether, propylene glycol dibutyl ether and the like, and these can be used alone or in combination.
[0030]
Examples of amines and amides include dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, pyridine, pyrazine and the like, and these can be used alone or in combination.
[0031]
Examples of the hydrocarbons include n-heptane, n-octane, n-decane, cyclohexane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, pinene and the like, and these can be used alone or in combination.
In addition, dimethyl sulfoxide and the like can be used.
These may be used in combination with a group other than the same group as long as the workability (including the drying property) and the resin properties are improved or impaired.
[0032]
In the present invention, a photosensitive polyimide film can be obtained by applying the photosensitive resin composition adjusted to a solid content of 10 to 90% by mass on a colorless and transparent film of a constant thickness at a constant thickness and drying.
[0033]
Here, as the colorless and transparent film, low-density polyethylene, high-density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, ethylene / cyclodecene copolymer (trade name: APEL, manufactured by Mitsui Chemicals, Inc.) and the like are used. Since the properties of polyamic acid change with moisture, resins having low moisture permeability are desirable. Therefore, among these, APEL (trademark), polyethylene, and polypropylene are preferable. Further, in consideration of coatability, adhesion, rollability, toughness, cost, etc., polyethylene, polypropylene, and APEL (trademark) having a high ethylene content having a film thickness of 15 to 100 μm, preferably 30 to 75 μm. Is more preferred.
[0034]
The photosensitive polyimide film can be applied to the above film by a known method such as a reverse roll coater, a gravure roll coater, a comma coater, and a curtain coater. Drying can be performed at a temperature of 50 to 120 ° C. by a hot air dryer or a dryer using far-infrared rays or near-infrared rays, and more preferably by drying at 60 to 100 ° C. for 10 to 60 minutes.
[0035]
The thickness of the photosensitive polyimide film is 5 to 100 μm, more preferably 10 to 50 μm. When the film thickness is 5 μm or more, there is no problem in insulation reliability, and when the film thickness is 100 μm or less, the resolution can be improved.
The photosensitive film is exposed through a photomask on which an arbitrary pattern is written to form fine holes and fine width lines. The exposure amount varies depending on the resin composition, but is usually 30 to 1000 mj / cm. 2 Therefore, lower energy and higher resolution are required. The actinic rays used at this time include, for example, electron beams, ultraviolet rays, X-rays and the like, and preferably ultraviolet rays. As a light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, or the like can be used. The film thus obtained is excellent in resistance to an acidic etching solution such as cupric chloride and ferric chloride used for etching a copper foil.
[0036]
Next, development is performed by a dipping method or a spray method using a developing solution. As the developer, an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous sodium carbonate solution can be used.
In this way, the copper-clad laminate on which the predetermined pattern is formed by the resist film is then used to dissolve and remove the copper foil in the portion without the resist film by using the above-mentioned etching solution, thereby forming a predetermined circuit pattern. Can be formed. After the circuit pattern is formed, it is removed with an alkaline solution such as sodium hydroxide.
[0037]
【Example】
Hereinafter, the present invention will be described in detail with reference to typical examples, but the present invention is not limited thereto.
(Synthesis example 1)
[Polyamic acid alkoxyalkyl ester PAE1]
In a reactor (with a stirrer, reflux condenser and nitrogen inlet tube), under nitrogen atmosphere, 350 g of N, N-dimethylacetamide, 291 g of diethylene glycol dimethyl ether, 173.2 g of 1,3-bis (3-aminophenoxy) benzene (0.1 g). 593 mol) was dissolved, and 126.8 g (0.582 mol) of pyromellitic dianhydride (molar ratio 0.981) was added little by little as a dry solid while stirring. During this period, the reaction temperature was maintained at 25 to 30 ° C, and stirring was continued for 10 hours under a nitrogen atmosphere after the addition. Next, the liquid temperature was raised to 50 to 60 ° C., and 59.0 g (0.590 mol) of isobutyl vinyl ether was added thereto over about 30 minutes. The reaction was further performed for 20 hours to obtain a polyamic acid isobutoxyethyl ester solution (PAE1) having a solid content of 35% by mass.
(Synthesis example 2)
[Polyamic acid alkoxyalkyl ester PAE2]
1,3-bis (3-aminophenoxy) biphenyl was used in place of 1,3-bis (3-aminophenoxy) benzene in Synthesis Example 1, and the same molar ratio (0.981) and reaction conditions as in Synthesis Example 1 were used. I went in. Further, 59.0 g (0.590 mol) of t-butyl vinyl ether was reacted in place of isobutyl vinyl ether to obtain a polyamic acid t-butoxyethyl ester solution (PAE2) having a solid content of 35% by mass.
[0038]
(Example 1)
200 parts by mass of PAE1 obtained in Synthesis Example 1 and 1.5 parts by mass of a photoacid generator diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate (manufactured by Wako, hereinafter referred to as WPAG-336) are mixed. It melt | dissolved and prepared the varnish. This varnish is applied as a carrier film having a width of 30 cm and a thickness of 20 μm on a polypropylene film at a thickness of about 100 μm, dried in a hot air circulating drying oven at 80 ° C. for 20 minutes, and a release film having a thickness of 20 μm is stuck to form a dry film. Produced. After peeling off the release film, the produced dry film was superimposed on the copper foil surface of the suspension base material (SUS / PI / Cu = 20/10/12 μm) on which the pattern was formed. Crimping was performed for 20 seconds. Next, the exposure amount is 100 mj / cm 2 1% Na kept at 30 ± 1 ° C after irradiation and peeling of the carrier film 2 CO 3 Was sprayed at 0.15 MPa, and then heat-cured at 250 ° C. for 10 minutes to provide a test piece for evaluation.
[0039]
(Example 2)
200 parts by mass of PAE2 obtained in Synthesis Example 2 and 2.5 parts by mass of a photoacid generator bis (cyclohexylsulfonyl) diazomethane (manufactured by Wako, hereinafter referred to as WPAG-145) were mixed and dissolved to prepare a varnish. This varnish is applied as a carrier film having a width of 30 cm and a thickness of 20 μm on a polypropylene film at a thickness of about 100 μm, dried in a hot air circulating drying oven at 80 ° C. for 20 minutes, and a cover film having a thickness of 20 μm is laminated to form a dry film. Produced. After peeling off the cover film, the prepared dry film was superimposed on a copper foil surface of a patterned suspension base material (SUS / PI / Cu = 20/10/12 μm), and after positioning, 100 ° C. with a vacuum laminating apparatus. Crimping was performed for 20 seconds. Next, the exposure amount is 100 mj / cm 2 1% Na kept at 30 ± 1 ° C after irradiation and peeling of the carrier film 2 CO 3 Was sprayed at 0.15 MPa, and then heat-cured at 250 ° C. for 10 minutes to provide a test piece for evaluation.
(Example 3)
200 parts by mass of PAE1 obtained in Synthesis Example 1, 1.5 parts by mass of photoacid generator diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate (manufactured by Wako, hereinafter referred to as WPAG-336) and bisphenol 18.0 parts by mass of A type epoxy resin R139S (trade name: manufactured by Mitsui Chemicals, Inc., EEW = 184 g / eq), phenol novolak resin PSM-4326 (manufactured by Gunei Chemical Industry Co., Ltd., OH equivalent = 104 g / eq) 10.0 parts by mass were mixed and dissolved to prepare a varnish. This varnish is applied as a carrier film having a width of 30 cm and a thickness of 20 μm on a polypropylene film to a thickness of about 100 μm, and then dried in a circulating hot air drying oven at 80 ° C. for 20 minutes. A cover film having a thickness of 20 μm is laminated and dried. A film was prepared. After peeling off the cover film, the prepared dry film was superimposed on a copper foil surface of a patterned suspension base material (SUS / PI / Cu = 20/10/12 μm), and after positioning, 100 ° C. with a vacuum laminating apparatus. Crimping was performed for 20 seconds. Next, the exposure amount is 100 mj / cm 2 1% Na kept at 30 ± 1 ° C after irradiation and peeling of the carrier film 2 CO 3 Was sprayed at 0.15 MPa, and then heat-cured at 250 ° C. for 10 minutes to provide a test piece for evaluation.
[0040]
(Comparative Example 1)
In a reactor (with a stirrer, reflux condenser and nitrogen introduction tube), under nitrogen atmosphere, 350 g of N, N-dimethylacetamide and 350 g of diethylene glycol dimethyl ether, 173.2 g of 1,3-bis (3-aminophenoxy) benzene (0.1 g). 593 mol) was dissolved, and 126.8 g (0.582 mol) of pyromellitic dianhydride (molar ratio 0.981) was added little by little as a dry solid while stirring. During this period, the reaction temperature was maintained at 25 to 30 ° C, and stirring was continued under a nitrogen atmosphere for 20 hours after the addition to obtain a polyamic acid solution (PA1) having a solid content of 30% by mass. This varnish is applied as a carrier film having a width of 30 cm and a thickness of 20 μm on a polypropylene film to a thickness of about 100 μm, and then dried in a circulating hot air drying oven at 80 ° C. for 20 minutes. A cover film having a thickness of 20 μm is laminated and dried. A film was prepared. After peeling off the cover film, the prepared dry film was superimposed on a copper foil surface of a patterned suspension base material (SUS / PI / Cu = 20/10/12 μm), and after positioning, 100 ° C. with a vacuum laminating apparatus. It was pressure-bonded for 20 seconds, heated and cured at 250 ° C. for 10 minutes, and supplied to a test piece for evaluation.
(Comparative Example 2)
601 g of 3,4′-diaminophenyl ether, 436 g of pyromellitic anhydride (acid value: 1011 mg KOH / g) and 1030 g of γ-butyrolactone are reacted at 40 ° C. × 5 hrs, and a polyamide prepolymer containing a terminal amine carboxyl group (acid value of solids) : 212.5 mg KOH / g). Next, 508 g of glycidyl methacrylate and 1.75 g of p-methoxyphenol were added and reacted at 95 ° C. × 10 Hrs to obtain a carboxyl group-containing polyamide oligomer (PO-1) having a solid content of 60% by mass. 150 g of this PO-1 was mixed with 20 g of a polyacrylate of dipentaerythritol ε-caprolactone adduct (trade name: DPCA-60, manufactured by Nippon Kayaku), 5.0 g of benzophenone as a photoinitiator, and 2.0 g of DETX, A photosensitive resin composition was obtained. This varnish is applied as a carrier film having a width of 30 cm and a thickness of 20 μm on a polypropylene film to a thickness of about 100 μm, and then dried in a circulating hot air drying oven at 80 ° C. for 20 minutes. A cover film having a thickness of 20 μm is laminated and dried. A film was prepared. After peeling off the cover film, the prepared dry film was superimposed on a copper foil surface of a patterned suspension base material (SUS / PI / Cu = 20/10/12 μm), and after positioning, 100 ° C. with a vacuum laminating apparatus. Crimping was performed for 20 seconds. Next, the exposure amount is 100 mj / cm 2 1% Na kept at 30 ± 1 ° C after irradiation and peeling of the carrier film 2 CO 3 Was sprayed at 0.15 MPa, and then heat-cured at 250 ° C. for 10 minutes to provide a test piece for evaluation.
[0041]
Using the dry films and test pieces for evaluation prepared in the above Examples and Comparative Examples, the following items were evaluated.
Evaluation 1 Resolution: 300 mj / cm 2 Exposure at 30 ± 1 ℃ 1.0% Na 2 CO 3 Aq was sprayed at a pressure of 0.15 Pa, developed, and cured (250 ° C. × 10 minutes) to determine whether or not the resolution was 100 μmφ or less in the via hole.
Evaluation 2 Cross cut peel: According to JIS K 5404.
Evaluation 3 Solder heat resistance: The molten solder held at ± 5 ° C. was floated with the resin surface down for 20 seconds. (Based on JPCA-BM02) The temperature was raised in steps of 10 ° C, and the temperature at which the film swelled or the like -10 ° C was taken as the measured value.
Evaluation 4 Tg: A cured film having a thickness of 30 to 35 μm, a width of 4 mm, and a length of 25 mm was prepared, and using TMA / SS100 manufactured by Seiko Denshi Co., Ltd., a tensile mode load of 5 g, a temperature rising rate of 2 ° C./min. Was measured.
Table 1 shows the evaluation results of Examples 1 to 3 and Comparative Examples 1 and 2.
[0042]
【Evaluation results】
[Table 1]
【The invention's effect】
The resin composition of the present invention can be developed with an aqueous alkali solution such as an aqueous sodium hydroxide solution and an aqueous sodium carbonate solution, and can form a fine image by low-energy exposure. Heat resistance, adhesion to a conductor, electrical characteristics, and the like.
Claims (2)
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| WO2015093271A1 (en) * | 2013-12-18 | 2015-06-25 | 富士フイルム株式会社 | Photosensitive transfer material, pattern formation method, and etching method |
| JP2015118202A (en) * | 2013-12-18 | 2015-06-25 | 富士フイルム株式会社 | Photosensitive transfer material, pattern forming method and etching method |
| US10108091B2 (en) | 2013-12-18 | 2018-10-23 | Fujifilm Corporation | Photosensitive transfer material, pattern formation method, and etching method |
| WO2024070808A1 (en) * | 2022-09-29 | 2024-04-04 | 味の素株式会社 | Photosensitive film and photosensitive resin composition |
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