JP2001348428A - Polyamic acid composition, soluble polyimide composition, and polybenzoxazole-polyimide composition - Google Patents
Polyamic acid composition, soluble polyimide composition, and polybenzoxazole-polyimide compositionInfo
- Publication number
- JP2001348428A JP2001348428A JP2000343220A JP2000343220A JP2001348428A JP 2001348428 A JP2001348428 A JP 2001348428A JP 2000343220 A JP2000343220 A JP 2000343220A JP 2000343220 A JP2000343220 A JP 2000343220A JP 2001348428 A JP2001348428 A JP 2001348428A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- hydrogen atom
- hydrocarbon group
- meth
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 24
- 229920001721 polyimide Polymers 0.000 title claims description 70
- 239000004642 Polyimide Substances 0.000 title claims description 39
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 41
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 32
- -1 acryloyloxyethyl Chemical group 0.000 claims abstract description 25
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 17
- 125000004185 ester group Chemical group 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 44
- 230000009102 absorption Effects 0.000 description 42
- 238000010521 absorption reaction Methods 0.000 description 42
- 238000003756 stirring Methods 0.000 description 42
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 37
- 239000002966 varnish Substances 0.000 description 35
- 239000007789 gas Substances 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 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 28
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 26
- 238000005259 measurement Methods 0.000 description 24
- 238000000862 absorption spectrum Methods 0.000 description 23
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 21
- 150000003949 imides Chemical class 0.000 description 21
- 238000011085 pressure filtration Methods 0.000 description 19
- 239000000758 substrate Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000010408 film Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 150000004984 aromatic diamines Chemical class 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 150000004985 diamines Chemical class 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229920002577 polybenzoxazole Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000010533 azeotropic distillation Methods 0.000 description 5
- 239000002981 blocking agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- QMQBBUPJKANITL-MYXGOWFTSA-N dextropropoxyphene hydrochloride Chemical compound [H+].[Cl-].C([C@](OC(=O)CC)([C@H](C)CN(C)C)C=1C=CC=CC=1)C1=CC=CC=C1 QMQBBUPJKANITL-MYXGOWFTSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000006358 imidation reaction Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- NMFFUUFPJJOWHK-UHFFFAOYSA-N 2-phenoxyaniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1 NMFFUUFPJJOWHK-UHFFFAOYSA-N 0.000 description 2
- NHJNWRVCOATWGF-UHFFFAOYSA-N 3-(3-amino-2-phenoxyphenyl)sulfonyl-2-phenoxyaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C(=C(N)C=CC=2)OC=2C=CC=CC=2)=C1OC1=CC=CC=C1 NHJNWRVCOATWGF-UHFFFAOYSA-N 0.000 description 2
- ULPWATNJVBJKGM-UHFFFAOYSA-N 3-[2-(3-amino-2-phenoxyphenyl)propan-2-yl]-2-phenoxyaniline Chemical compound C=1C=CC(N)=C(OC=2C=CC=CC=2)C=1C(C)(C)C1=CC=CC(N)=C1OC1=CC=CC=C1 ULPWATNJVBJKGM-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- DLEPYXFUDLQGDW-UHFFFAOYSA-N FC(F)(F)NC1=CC=C(C2=CC=C(NC(F)(F)F)C=C2)C=C1 Chemical compound FC(F)(F)NC1=CC=C(C2=CC=C(NC(F)(F)F)C=C2)C=C1 DLEPYXFUDLQGDW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-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
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- SZKKRCSOSQAJDE-UHFFFAOYSA-N Schradan Chemical group CN(C)P(=O)(N(C)C)OP(=O)(N(C)C)N(C)C SZKKRCSOSQAJDE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GGQKSERDXSAHCN-UHFFFAOYSA-N [dimethoxy(methyl)silyl] 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)OC(=O)C(C)=C GGQKSERDXSAHCN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FYBYQXQHBHTWLP-UHFFFAOYSA-N bis(silyloxysilyloxy)silane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH2]O[SiH3] FYBYQXQHBHTWLP-UHFFFAOYSA-N 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- YNDRMAAWTXUJPV-UHFFFAOYSA-N n-cyclohexyl-2-methylidenecyclohexan-1-amine Chemical compound C=C1CCCCC1NC1CCCCC1 YNDRMAAWTXUJPV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリアミド酸組成
物およびポリベンゾオキサゾール−ポリイミド組成物に
係り、特に低い誘電率を有する材料に関する。The present invention relates to a polyamic acid composition and a polybenzoxazole-polyimide composition, and more particularly to a material having a low dielectric constant.
【０００２】[0002]
【従来の技術】大型計算機の演算処理速度は、素子の高
速化、実装系の高密度化によって高速化の一途をたどっ
ている。これに対し、実装基板の信号層に用いる絶縁材
料の低誘電化の要求も高まっている。この理由は、絶縁
膜の誘電率が低ければ低い程、下記（Ｉ）式に示す関係
により、信号伝播遅延が低減され、その結果、演算処理
速度の高速化が見込めるからである。2. Description of the Related Art The arithmetic processing speed of a large-scale computer has been steadily increasing due to an increase in the speed of elements and an increase in the density of a mounting system. On the other hand, there is an increasing demand for lowering the dielectric constant of the insulating material used for the signal layer of the mounting board. The reason is that the lower the dielectric constant of the insulating film, the lower the signal propagation delay due to the relationship shown in the following equation (I), and as a result, the higher the processing speed can be expected.
【０００３】Ｔｄ＝ｌ（ε）0.5 （Ｉ） Ｔｄ：信号伝播遅延時間、ｌ：回路定数、ε：絶縁層の
比誘電率。Td = 1 (ε) 0.5 (I) Td: signal propagation delay time, l: circuit constant, ε: relative dielectric constant of the insulating layer.
【０００４】具体的な方法として、従来絶縁層に用いら
れていたセラミックス（εは約１０）を、有機材料（ε
＝２〜６）に替える試みがなされている。その材料とし
ては、実装基板製造時の薄膜プロセス、並びに、チップ
接続、ピン付等の後工程に耐えられる優れた耐熱性を有
する、例えば米国特許第３１７９６３４号記載のポリイ
ミド系樹脂が着目されている。As a specific method, ceramics (ε is about 10) conventionally used for an insulating layer are replaced with an organic material (ε).
= 2 to 6). As the material, for example, a polyimide resin described in U.S. Pat. No. 3,179,634, which has excellent heat resistance that can withstand a thin film process at the time of manufacturing a mounting substrate and post-processes such as chip connection and pin attachment, has been noted. .
【０００５】この中でも、低比誘電率のポリイミドとし
ては、サーミッドＦＡ−７００１（（株）カネボウエヌ
エスシー）が、ε＝２．９５（１０ｋＨｚ、カタログ
値）という値で、市販品の中で低い値を有している。[0005] Among them, as a polyimide having a low relative dielectric constant, THERmid FA-7001 (Kanebo uenu SSC) has a value of ε = 2.95 (10 kHz, catalog value), which is the lowest among commercially available products. Have a value.
【０００６】[0006]
【発明が解決しようとする課題】しかし、上記ポリイミ
ド系樹脂にあっても、演算処理速度の高速化に伴い、さ
らに比誘電率の低いものが要求されてきているのが実情
である。すなわち、計算機用薄膜多層基板に代表され
る、高速信号処理が求められる基板や、素子の絶縁層に
好適な材料として、低比誘電率で、しかも、耐熱性の優
れた材料が要求されている。However, even in the case of the above-mentioned polyimide resin, a resin having a lower relative dielectric constant has been demanded in accordance with an increase in the processing speed. In other words, as a material suitable for a substrate requiring high-speed signal processing, such as a thin-film multilayer substrate for a computer, or an insulating layer of an element, a material having a low dielectric constant and excellent heat resistance is required. .
【０００７】本発明の目的は、このような要求に沿っ
た、従来より低誘電率で、かつ、従来と同等の耐熱性を
有して、高速信号処理が求められる基板や、素子の絶縁
層に好適な材料とその製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to meet the above-mentioned requirements and to provide a substrate having a lower dielectric constant than the conventional one and having the same heat resistance as the conventional one and for which high-speed signal processing is required, and an insulating layer of an element. And a method for manufacturing the same.
【０００８】[0008]
【課題を解決するための手段】上記目的は、下記の一般
式（１）で表される繰り返し単位からなることを特徴と
するポリアミド酸組成物であり、一般式（３）で表され
る繰り返し単位からなることを特徴とする可溶性ポリイ
ミド組成物であり、一般式（３）、一般式（５）、一般
式（６）、一般式（７）のいずれかで構成されることを
特徴とするポリベンゾオキサゾール−ポリイミド組成物
である。An object of the present invention is to provide a polyamic acid composition comprising a repeating unit represented by the following general formula (1), wherein the repeating unit represented by the general formula (3) A soluble polyimide composition comprising a unit, characterized by being constituted by any of the general formula (3), the general formula (5), the general formula (6), and the general formula (7). It is a polybenzoxazole-polyimide composition.
【０００９】[0009]
【化６】 Embedded image
【００１０】（式中、Ｒ１、Ｒ２はメチレン、酸素、C
(CH3)2、C(CF3)2、COOのうちのいずれかの基を示す。Ｒ
３は水素原子、炭素数１から１０までの炭化水素基、
（メタ）アクリロイルオキシエチル基、（メタ）アクリ
ロイルオキシｎ−プロピル基、（メタ）アクリロイルオ
キシｉ−プロピル基、（メタ）アクリロイルオキシｎ−
ブチル基のうちのいずれかの基を示す。Ｒ４は水素原
子、炭素数１から４までの炭化水素基、炭素数１から４
までのアルコキシ基、エステル基、カルボキシル基、水
酸基を示す。Ｒ５は水素原子、炭素数１から６までの炭
化水素基、Ｒ６−ＣＯ基、Ｒ６−ＯＣＯ基を示す。Ｒ６
は水素原子、炭素数１から４までの炭化水素基を示す。
ｐ、ｑは０から２までの整数を示す。ｒ、ｓは０または
１を示す。）(Wherein R1 and R2 are methylene, oxygen, C
It represents any of (CH 3 ) 2 , C (CF 3 ) 2 and COO. R
3 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms,
(Meth) acryloyloxyethyl group, (meth) acryloyloxy n-propyl group, (meth) acryloyloxy i-propyl group, (meth) acryloyloxy n-
Shows any of the butyl groups. R4 is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
Up to an alkoxy group, an ester group, a carboxyl group, and a hydroxyl group. R5 represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an R6-CO group, or an R6-OCO group. R6
Represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
p and q each represent an integer from 0 to 2. r and s represent 0 or 1. )
【００１１】[0011]
【化７】 Embedded image
【００１２】（式中、Ｒ１、Ｒ２はメチレン、酸素、C
(CH3)2、C(CF3)2、COOのうちのいずれかの基を示す。Ｒ
４は水素原子、炭素数１から４までの炭化水素基、炭素
数１から４までのアルコキシ基、エステル基、カルボキ
シル基、水酸基を示す。Ｒ５は水素原子、炭素数１から
６までの炭化水素基、Ｒ６−ＣＯ基、Ｒ６−ＯＣＯ基を
示す。Ｒ６は炭素数１から４までの炭化水素基を示す。
ｐ、ｑは０から２までの整数を示す。ｒ、ｓは０または
１を示す。）(Wherein R1 and R2 are methylene, oxygen, C
It represents any of (CH 3 ) 2 , C (CF 3 ) 2 and COO. R
4 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an ester group, a carboxyl group, or a hydroxyl group. R5 represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an R6-CO group, or an R6-OCO group. R6 represents a hydrocarbon group having 1 to 4 carbon atoms.
p and q each represent an integer from 0 to 2. r and s represent 0 or 1. )
【００１３】[0013]
【化８】 Embedded image
【００１４】（式中、Ｒ１、Ｒ２はメチレン、酸素、C
(CH3)2、C(CF3)2、COOのうちのいずれかの基を示す。Ｒ
４は水素原子、炭素数１から４までの炭化水素基、炭素
数１から４までのアルコキシ基、エステル基、カルボキ
シル基、水酸基を示す。Ｒ５は水素原子、炭素数１から
６までの炭化水素基、Ｒ６−ＣＯ基、Ｒ６−ＯＣＯ基を
示す。Ｒ６は水素原子、炭素数１から４までの炭化水素
基を示す。ただし、Ｒ４が水酸基、炭素数１から４まで
のアルコキシ基、エステル基以外の基を表す場合、一般
式（５）及び一般式（６）であり、Ｒ４が水酸基、炭素
数１から４までのアルコキシ基、エステル基の場合は、
一般式（７）及び一般式（８）となる。ｐ、ｑは０から
２までの整数を示す。ｒ、ｓは０または１を示す。）(Wherein R1 and R2 are methylene, oxygen, C
It represents any of (CH 3 ) 2 , C (CF 3 ) 2 and COO. R
4 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an ester group, a carboxyl group, or a hydroxyl group. R5 represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an R6-CO group, or an R6-OCO group. R6 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. However, when R4 represents a group other than a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and an ester group, they are represented by the general formulas (5) and (6), and R4 is a hydroxyl group, a group having 1 to 4 carbon atoms. In the case of an alkoxy group or an ester group,
The general formulas (7) and (8) are obtained. p and q each represent an integer from 0 to 2. r and s represent 0 or 1. )
【００１５】[0015]
【発明の実施の形態】本発明は、一般式（１）で表され
るポリアミド酸や、一般式（３）で表される可溶性ポリ
イミドを熱硬化し、一般式（３）及び一般式（５）で表
されるポリベンゾオキサゾール−ポリイミド、または一
般式（３）及び一般式（６）及び一般式（７）で表され
るポリベンゾオキサゾール−ポリイミド、または一般式
（６）及び一般式（７）で表されるポリベンゾオキサゾ
ール−ポリイミドに変換することによって、上記目的を
達成するものである。また、一般式（２）で表されるポ
リアミド酸、及び一般式（４）で表される可溶性ポリイ
ミドも上記目的を達成できるものである。BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a polyamic acid represented by the general formula (1) or a soluble polyimide represented by the general formula (3) is heat-cured to obtain the compound represented by the general formula (3) or (5). ) Or a polybenzoxazole-polyimide represented by the general formulas (3), (6) and (7), or a general formula (6) and the general formula (7) The above object is achieved by converting into polybenzoxazole-polyimide represented by the formula (1). The polyamic acid represented by the general formula (2) and the soluble polyimide represented by the general formula (4) can also achieve the above object.
【００１６】本発明における一般式（１）及び一般式
（２）で表されるポリアミド酸または、一般式（３）及
び一般式（４）で表される可溶性ポリイミドのＲ１、Ｒ
２は、メチレン、酸素、C(CH3)2、C(CF3)2、COOのうち
のいずれかの基を示し、好ましくは、酸素、C(CH3)2、C
(CF3)2である。また、Ｒ３は水素原子、炭素数１から１
０までの炭化水素基、（メタ）アクリロイルオキシエチ
ル基、（メタ）アクリロイルオキシｎ−プロピル基、
（メタ）アクリロイルオキシｉ−プロピル基、（メタ）
アクリロイルオキシｎ−ブチル基のうちのいずれかの基
を示し、好ましくは、水素原子、炭素数１から４までの
炭化水素基、（メタ）アクリロイルオキシエチル基、
（メタ）アクリロイルオキシｎ−プロピル基、（メタ）
アクリロイルオキシｉ−プロピル基である。Ｒ４は水素
原子、炭素数１から４までの炭化水素基、炭素数１から
４までのアルコキシ基、エステル基、カルボキシル基、
水酸基を示し、好ましくは、水素原子、メチル基、エチ
ル基、アセトキシ基、カルボキシル基、メトキシ基、エ
トキシ基、ｔ−ブトキシ基、水酸基である。Ｒ５は水素
原子、炭素数１から６までの炭化水素基、Ｒ６−ＣＯ
基、Ｒ６−ＯＣＯ基を示し、好ましくは、水素原子、メ
チル基、エチル基、ｔ−ブチル基、Ｒ６−ＣＯ基、Ｒ６
−ＯＣＯ基である。Ｒ６は、水素原子、炭素数１から４
までの炭化水素基を示し、好ましくは、水素原子、メチ
ル基、エチル基、ｔ−ブチル基である。In the present invention, R1 and R of the polyamic acid represented by the general formulas (1) and (2) or the soluble polyimide represented by the general formulas (3) and (4) are used.
2 represents any one of methylene, oxygen, C (CH 3 ) 2 , C (CF 3 ) 2 and COO, preferably oxygen, C (CH 3 ) 2 , C
(CF 3 ) 2 . R3 is a hydrogen atom, having 1 to 1 carbon atoms.
Hydrocarbon groups up to 0, (meth) acryloyloxyethyl groups, (meth) acryloyloxy n-propyl groups,
(Meth) acryloyloxy i-propyl group, (meth)
An acryloyloxy n-butyl group, preferably a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a (meth) acryloyloxyethyl group,
(Meth) acryloyloxy n-propyl group, (meth)
An acryloyloxy i-propyl group. R4 is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an ester group, a carboxyl group,
It represents a hydroxyl group, preferably a hydrogen atom, a methyl group, an ethyl group, an acetoxy group, a carboxyl group, a methoxy group, an ethoxy group, a t-butoxy group, or a hydroxyl group. R5 is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, R6-CO
A hydrogen atom, a methyl group, an ethyl group, a t-butyl group, a R6-CO group, or a R6 group.
—OCO group. R6 is a hydrogen atom, having 1 to 4 carbon atoms
And preferably a hydrogen atom, a methyl group, an ethyl group or a t-butyl group.
【００１７】本発明における一般式（１）及び一般式
（２）で表されるポリアミド酸は、Ｎ，Ｎ−ジメチルア
セトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチ
ル−２−ピロリドン、ジグライム、γーブチロラクトン
等の極性溶媒中で、ジアミンとテトラカルボン酸二無水
物の重合反応により製造すればよい。The polyamic acids represented by the general formulas (1) and (2) in the present invention include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, diglyme, γ It may be produced by a polymerization reaction of a diamine and a tetracarboxylic dianhydride in a polar solvent such as butyrolactone.
【００１８】本発明における、一般式（３）及び一般式
（４）で表されるポリイミドは、Ｎ，Ｎ−ジメチルアセ
トアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル
−２−ピロリドン、ジグライム、γーブチロラクトン等
の極性溶媒中で、ジアミンとテトラカルボン酸二無水物
の重合反応により、一旦、ポリアミド酸溶液を製造し、
これに、無水酢酸／ピリジンを添加してイミド化する”
化学イミド法”あるいは、一旦製造したポリアミド酸溶
液にトルエンを添加し、トルエン共沸によって加熱脱水
してイミド化する”熱イミド化法”によって製造すれば
よい。In the present invention, the polyimides represented by the general formulas (3) and (4) include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, diglyme, γ In a polar solvent such as butyrolactone, by a polymerization reaction of diamine and tetracarboxylic dianhydride, once, to produce a polyamic acid solution,
To this, acetic anhydride / pyridine is added to imidize. "
It may be produced by a chemical imidization method or a “thermal imidization method” in which toluene is added to a polyamic acid solution once produced, and the mixture is heated and dehydrated by azeotropic distillation with toluene to undergo imidization.
【００１９】本発明で使用されるジアミンとしては、ア
ミノ基のオルト位に酸素原子を有するものであれば良
く、好ましい化合物は下記に挙げられる。The diamine used in the present invention may be any diamine having an oxygen atom at the ortho position of the amino group, and preferred compounds are listed below.
【００２０】[0020]
【化９】 Embedded image
【００２１】さらに好ましい化合物は下記に挙げられ
る。Further preferred compounds are listed below.
【００２２】[0022]
【化１０】 Embedded image
【００２３】もし、アミノ基のオルト位に酸素原子が無
ければ、熱硬化時に、イミドの生成だけがおこり、ベン
ゾオキサゾールは生成しないため好ましくない。If there is no oxygen atom at the ortho-position of the amino group, only imide is generated during thermal curing, and benzoxazole is not generated, which is not preferable.
【００２４】また、１〜４０モル％の範囲の、他のジア
ミン成分を用いて変性することもできる。これらの例と
しては、フェニレンジアミン、ジアミノジフェニルエー
テル、アミノフェノキシベンゼン、ジアミノジフェニル
メタン、ジアミノジフェニルスルホン、ビス（トリフル
オロメチル）ベンチジン、ビス（アミノフェノキシフェ
ニル）プロパン、ビス（アミノフェノキシフェニル）ス
ルホンあるいはこれらの芳香族環にアルキル基やハロゲ
ン原子で置換した化合物などを挙げることができる。こ
のような例として、フェニレンジアミン、ジアミノジフ
ェニルエーテル、アミノフェノキシベンゼン、ジアミノ
ジフェニルメタン、ジアミノジフェニルスルホン、ビス
（トリフルオロメチル）ベンチジン、ビス（アミノフェ
ノキシフェニル）プロパン、ビス（アミノフェノキシフ
ェニル）スルホンあるいはこれらの芳香族環にアルキル
基やハロゲン原子で置換した化合物など、脂肪族のシク
ロヘキシルジアミン、メチレンビスシクロヘキシルアミ
ンなどが挙げられる。このようなジアミン成分を４０モ
ル％以上共重合すると得られるポリマーの誘電率が高く
なる恐れがある。Further, it can be modified with another diamine component in the range of 1 to 40 mol%. Examples of these include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone and their aromatics. Examples thereof include compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom. Such examples include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, and aromatics thereof. Aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like, such as compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom, may be mentioned. When such a diamine component is copolymerized in an amount of 40 mol% or more, the dielectric constant of the obtained polymer may be increased.
【００２５】さらに、基板との接着性を向上させるため
に、耐熱性を低下させない範囲で、ジアミン成分とし
て、ビス（３−アミノプロピル）テトラメチルジシロキ
サン、ビス（ｐ−アミノ−フェニル）オクタメチルペン
タシロキサンなどを１〜１０モル％共重合することもで
きる。Further, in order to improve the adhesiveness to the substrate, bis (3-aminopropyl) tetramethyldisiloxane and bis (p-amino-phenyl) octamethyl are used as diamine components within a range that does not lower the heat resistance. Pentasiloxane or the like can be copolymerized at 1 to 10 mol%.
【００２６】上記テトラカルボン酸二無水物としては、
下記の化合物が好ましいものとして挙げられる。As the above tetracarboxylic dianhydride,
The following compounds are preferred.
【００２７】[0027]
【化１１】 Embedded image
【００２８】特に好ましい化合物は下記に挙げたもので
ある。Particularly preferred compounds are those listed below.
【００２９】[0029]
【化１２】 Embedded image
【００３０】また、１〜４０モル％の範囲の、他の酸二
無水物成分を用いて変性することもできる。これらの例
としては、ベンゾフェノンテトラカルボン酸、ジフェニ
ルスルホンテトラカルボン酸などの芳香族テトラカルボ
ン酸、ブタンテトラカルボン酸、シクロペンタンテトラ
カルボン酸などの脂肪族のテトラカルボン酸などを挙げ
ることができる。このような酸二無水物成分を４０モル
％以上共重合すると得られるポリマーの誘電率が高くな
る恐れがある。Further, it can be modified with another acid dianhydride component in the range of 1 to 40 mol%. Examples thereof include aromatic tetracarboxylic acids such as benzophenonetetracarboxylic acid and diphenylsulfonetetracarboxylic acid, and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid. If such an acid dianhydride component is copolymerized in an amount of 40 mol% or more, the resulting polymer may have a high dielectric constant.
【００３１】また、必要に応じて上記、本発明の材料と
基板との塗れ性を向上させる目的で界面活性剤、乳酸エ
チルやプロピレングリコールモノメチルエーテルアセテ
ートなどのエステル類、エタノールなどのアルコール
類、シクロヘキサノン、メチルイソブチルケトンなどの
ケトン類、テトラヒドロフラン、ジオキサンなどのエー
テル類を混合しても良い。また、２酸化ケイ素、２酸化
チタンなどの無機粒子、あるいはポリイミドの粉末など
を添加することもできる。If necessary, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, and cyclohexanone for the purpose of improving the wettability between the material of the present invention and the substrate. And ketones such as methyl isobutyl ketone and ethers such as tetrahydrofuran and dioxane. In addition, inorganic particles such as silicon dioxide and titanium oxide, or powder of polyimide can also be added.
【００３２】さらにシリコンウエハーなどの下地基板と
の接着性を高めるために、シランカップリング剤、チタ
ンキレート剤などを本発明の材料に０．５から１０重量
％添加したり、下地基板をこのような薬液で前処理した
りすることもできる。In order to further enhance the adhesion to the underlying substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent or the like is added to the material of the present invention in an amount of 0.5 to 10% by weight. It can also be pre-treated with an appropriate chemical solution.
【００３３】添加する場合、メチルメタクリロキシジメ
トキシシラン、３−アミノプロピルトリメトキシシラ
ン、などのシランカップリング剤、チタンキレート剤、
アルミキレート剤をワニス中のポリマーに対して０．５
から１０重量％添加する。When added, a silane coupling agent such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, a titanium chelating agent,
An aluminum chelating agent was added to the polymer in the varnish in an amount of 0.5%.
To 10% by weight.
【００３４】基板を処理する場合、上記で述べたカップ
リング剤をイソプロパノール、エタノール、メタノー
ル、水、テトラヒドロフラン、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
ノメチルエーテル、乳酸エチル、アジピン酸ジエチルな
どの溶媒に０．５から２０重量％溶解させた溶液をスピ
ンコート、浸漬、スプレー塗布、蒸気処理などで表面処
理をする。場合によっては、その後５０℃から３００℃
までの温度をかけることで、基板と上記カップリング剤
との反応を進行させる。When treating the substrate, the above-described coupling agent is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate and the like. The solution in which 5 to 20% by weight is dissolved is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment, or the like. In some cases, then 50 ° C to 300 ° C
The reaction between the substrate and the coupling agent proceeds by applying a temperature up to
【００３５】また、本発明の一般式（３）で表されるポ
リイミドは、上記の方法の他に一般式（１）で表される
ポリアミド酸の分子量を調節し、熱処理、化学処理等を
することによってもで得られるが、一般式（３）で表さ
れるポリイミドが、前記に示す合成溶剤を含む有機溶剤
に対して、可溶性であるためには、重量平均分子量が、
ポリスチレン換算で３０００〜９００００であることが
好ましく、さらに好ましくは、５０００〜６００００で
ある。また一般式（４）で表されるポリイミドも同様
に、一般式（２）で表されるポリアミド酸から、上記の
方法で得ることができる。The polyimide of the present invention represented by the general formula (3) is subjected to a heat treatment, a chemical treatment and the like by adjusting the molecular weight of the polyamic acid represented by the general formula (1) in addition to the above method. However, in order for the polyimide represented by the general formula (3) to be soluble in the organic solvent including the synthetic solvent described above, the weight average molecular weight is
It is preferably from 3000 to 90000 in terms of polystyrene, more preferably from 5000 to 60000. Similarly, the polyimide represented by the general formula (4) can be obtained from the polyamic acid represented by the general formula (2) by the above method.
【００３６】さらに、この分子量調節には例えば、以下
のような末端封止剤が用いられるが分子量調節機能があ
れば特に限定されるものではない。Further, for controlling the molecular weight, for example, the following terminal blocking agent is used, but there is no particular limitation as long as it has a molecular weight controlling function.
【００３７】[0037]
【化１３】 Embedded image
【００３８】式中、Ｒ７はH、CH3、C2H5、COOH、COOC
H3、COOC2H5、OH、のうちのいずれかの基を示す。Wherein R7 is H, CH 3 , C 2 H 5 , COOH, COOC
H 3 , COOC 2 H 5 , or OH.
【００３９】分子量調節剤の添加量としては、ジアミン
成分に対して０．１〜５０モル％の範囲が好ましく、特
に好ましくは１〜４０モル％である。The amount of the molecular weight regulator to be added is preferably in the range of 0.1 to 50 mol%, more preferably 1 to 40 mol%, based on the diamine component.
【００４０】このようにして製造された一般式（１）で
表されるポリアミド酸、または一般式（３）で表される
可溶性ポリイミドは、熱硬化によって、本発明における
一般式（３）及び一般式（５）で表されるポリベンゾオ
キサゾール−ポリイミド、あるいは一般式（３）及び一
般式（６）および一般式（７）で表されるポリベンゾオ
キサゾール−ポリイミド、あるいは一般式（６）および
一般式（７）で表されるポリベンゾオキサゾール−ポリ
イミドのいずれかに変換されるものである。The polyamic acid represented by the general formula (1) or the soluble polyimide represented by the general formula (3) thus produced is cured by thermosetting to obtain the polyamic acid represented by the general formula (3) according to the present invention. Polybenzoxazole-polyimide represented by the formula (5), or polybenzoxazole-polyimide represented by the general formula (3) and the general formula (6) and the general formula (7), or the general formula (6) and the general It is converted into any of the polybenzoxazole-polyimides represented by the formula (7).
【００４１】本発明における一般式（５）、一般式
（６）、一般式（７）で表される化合物のＲ１、Ｒ２
は、メチレン、酸素、C(CH3)2、C(CF3)2、COOのうちの
いずれかの基を示し、好ましくは、酸素、C(CH3)2、C(C
F3)2である。また、Ｒ４は水素原子、炭素数１から４ま
での炭化水素基、炭素数１から４までのアルコキシ基、
エステル基、カルボキシル基、水酸基を示し、好ましく
は、水素原子、メチル基、エチル基、アセトキシ基、カ
ルボキシル基、メトキシ基、エトキシ基、ｔ−ブトキシ
基、水酸基である。Ｒ５は水素原子、炭素数１から６ま
での炭化水素基、Ｒ６−ＣＯ基、Ｒ６−ＯＣＯ基を示
し、好ましくは、水素原子、メチル基、エチル基、ｔ−
ブチル基、Ｒ６−ＣＯ基、Ｒ６−ＯＣＯ基である。Ｒ６
は、水素原子、炭素数１から４までの炭化水素基を示
し、好ましくは、水素原子、メチル基、エチル基、ｔ−
ブチル基である。In the present invention, R1 and R2 of the compounds represented by the general formulas (5), (6) and (7)
Represents a group of methylene, oxygen, C (CH 3 ) 2 , C (CF 3 ) 2 , COO, and preferably represents oxygen, C (CH 3 ) 2 , C (C
F 3 ) 2 . R4 is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
It represents an ester group, a carboxyl group, or a hydroxyl group, and is preferably a hydrogen atom, a methyl group, an ethyl group, an acetoxy group, a carboxyl group, a methoxy group, an ethoxy group, a t-butoxy group, or a hydroxyl group. R5 represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an R6-CO group, or an R6-OCO group, preferably a hydrogen atom, a methyl group, an ethyl group, or a t-
A butyl group, an R6-CO group, and an R6-OCO group. R6
Represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and is preferably a hydrogen atom, a methyl group, an ethyl group,
It is a butyl group.
【００４２】また、一般式（３）および一般式（５）
は、Ｒ４が水酸基、炭素数１から４までのアルコキシ
基、エステル基以外の基を表す場合にとりうる構造であ
り、一般式（３）及び一般式（６）及び一般式（７）、
あるいは一般式（６）及び一般式（７）は、Ｒ４が水酸
基、炭素数１から４までのアルコキシ基、エステル基を
表す場合にとりうる構造である。Further, the general formulas (3) and (5)
Is a structure that can be taken when R4 represents a group other than a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and an ester group, and is represented by the general formulas (3), (6) and (7),
Alternatively, the general formulas (6) and (7) are structures that can be taken when R4 represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or an ester group.
【００４３】本発明のポリベンゾオキサゾール−ポリイ
ミド組成物は、ベンゾオキサゾールとイミドの両方が存
在することにより、ベンゾオキサゾール由来の低誘電率
と、ポリイミド由来の耐溶剤性及び基板接着性を併せ持
つ。The polybenzoxazole-polyimide composition of the present invention has both a low dielectric constant derived from benzoxazole, solvent resistance derived from polyimide, and substrate adhesion due to the presence of both benzoxazole and imide.
【００４４】次に、本発明の材料を熱硬化し、成膜する
方法について説明する。前記の方法で合成された本発明
のポリアミド酸溶液及び／または本発明のポリイミド溶
液を基板上に塗布する。基板としては、ガラス基盤、シ
リコンウエハー、セラミックス類、ガリウムヒ素などが
用いられるが、これらに限定されない。塗布方法として
はスピンナを用いた回転塗布、スプレー塗布、ロールコ
ーティングなどの方法がある。また、塗布膜厚は、塗布
手法、組成物の固形分濃度、粘度などによって異なるが
通常、乾燥後の膜厚が、０．１から１５０μｍになるよ
うに塗布される。Next, a method for thermally curing the material of the present invention to form a film will be described. The polyamic acid solution of the present invention and / or the polyimide solution of the present invention synthesized by the above method is applied on a substrate. As the substrate, a glass substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The thickness of the coating varies depending on the coating method, the solid concentration of the composition, the viscosity, and the like, but the coating is usually applied so that the thickness after drying is 0.1 to 150 μm.
【００４５】次に本発明の材料を塗布した基板を乾燥し
て、皮膜を得る。乾燥はオーブン、ホットプレート、赤
外線などを使用し、４０度から７００度の範囲で１分か
ら１０時間行うのが好ましい。特に３００度から６００
度の範囲で３０分から８時間行うのが好ましい。また、
熱硬化して得られた膜はの平行方向の屈折率（ＴＥ）
は、１．５９５から１．３６７好ましく、特に好ましく
は、１．５００から１．４００である。Next, the substrate coated with the material of the present invention is dried to obtain a film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at a temperature in the range of 40 to 700 degrees for 1 minute to 10 hours. Especially 300 to 600 degrees
It is preferable to carry out for 30 minutes to 8 hours in the range of degrees. Also,
The film obtained by thermosetting has a parallel refractive index (TE)
Is preferably from 1.595 to 1.367, particularly preferably from 1.500 to 1.400.
【００４６】熱硬化膜の５％重量減少温度（Ｔｄ５）
は、５００℃から６５０℃が好ましく、特に好ましく
は、５１０℃から５９０℃である。5% weight loss temperature of thermosetting film (Td5)
Is preferably from 500 ° C. to 650 ° C., particularly preferably from 510 ° C. to 590 ° C.
【００４７】熱硬化膜の比誘電率（ε）は、２．８５か
ら２．００好ましく、特に好ましくは、２．８０から
２．１０である。The relative permittivity (ε) of the thermosetting film is preferably from 2.85 to 2.00, particularly preferably from 2.80 to 2.10.
【００４８】[0048]
【実施例】以下、本発明をより詳細に説明するために、
実施例及び比較例をあげて説明するが、本発明はこれら
の例によって限定されるものではない。EXAMPLES Hereinafter, in order to explain the present invention in more detail,
The present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００４９】特性の測定方法 膜厚の測定 シリコンウエハーに製膜した膜に傷を付け、その傷の深
さを測定し、その深さを膜の厚さとした。Method of Measuring Characteristics Measurement of Film Thickness A film formed on a silicon wafer was scratched, the depth of the scratch was measured, and the depth was defined as the film thickness.
【００５０】比誘電率の測定 膜の１ｋＨｚにおける静電容量を、（株）横川ヒューレ
ットパッカード製のＬＣＲメータ４２８４Ａで測定し、
下記の式（II）を用いて比誘電率εを求めた。測定周波
数は１ｋＨｚを用いた。 ε＝ｃ・ｄ／ε0・Ｓ （II） （ｃ：静電容量、ｄ：試料膜厚、ε0：真空の誘電率、
Ｓ：上部電極面積）。Measurement of relative permittivity The capacitance of the film at 1 kHz was measured with an LCR meter 4284A manufactured by Yokogawa Hewlett-Packard Co., Ltd.
The relative dielectric constant ε was determined using the following equation (II). The measurement frequency used was 1 kHz. ε = cd / ε0 · S (II) (c: capacitance, d: sample thickness, ε0: dielectric constant in vacuum,
S: upper electrode area).
【００５１】屈折率の測定 Ｈｅ−Ｎｅレーザーの波長６３３ｎｍを用い、プリズム
カップラー法で２０℃で測定し、膜面に対して、平行方
向の屈折率（ＴＥ）を測定した。 赤外吸収スペクトル（ＩＲ）測定 シリコンウエハーに製膜した膜を（株）堀場製作所製の
ＦＴ−７２０を用いてそのまま測定した。 ５％重量減少温度（Ｔｄ５） （株）島津製作所製の熱重量測定装置ＴＧＡ−５０によ
り窒素雰囲気中、昇温速度１０℃／分で測定した。Measurement of Refractive Index Using a He-Ne laser at a wavelength of 633 nm, the refractive index was measured at 20 ° C. by the prism coupler method, and the refractive index (TE) in the direction parallel to the film surface was measured. Infrared absorption spectrum (IR) measurement The film formed on the silicon wafer was directly measured using FT-720 manufactured by Horiba, Ltd. 5% Weight Loss Temperature (Td5) Measured at a heating rate of 10 ° C./min in a nitrogen atmosphere using a thermogravimeter TGA-50 manufactured by Shimadzu Corporation.
【００５２】実施例１ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したＮ，Ｎ−ジメチルアセトアミドを
１５０ｇ入れ、下記（ａ）式で表される芳香族ジアミン
（（株）セントラル硝子製）２５．４９ｇ（６９．６ｍ
ｍｏｌ）を加え完全に溶解した。Example 1 A 500 mL four-necked flask as a reaction vessel was equipped with a stirring rod with a blade, a cooling pipe, and a N 2 gas introduction pipe, and then dried N 2 gas was flowed. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled N, N-dimethylacetamide was added, and 25.49 g (69.6 m) of an aromatic diamine represented by the following formula (a) (manufactured by Central Glass Co., Ltd.)
mol) was completely dissolved.
【００５３】[0053]
【化１４】 Embedded image
【００５４】この後、フラスコをウオーターバスにつ
け、下記（ｂ）式で表されるテトラカルボン酸二無水物
（（株）ダイキン工業製）３４．０１ｇ（７６．５５ｍ
ｍｏｌ）を反応液の温度が６０℃以上にならないよう少
量ずつ加えた。この際、反応容器壁についた下記テトラ
カルボン酸二無水物をＮ，Ｎ−ジメチルアセトアミド５
０ｇで洗い流しながら加えた。Thereafter, the flask was placed in a water bath, and 34.01 g (76.55 m) of tetracarboxylic dianhydride (manufactured by Daikin Industries, Ltd.) represented by the following formula (b):
mol) was added little by little so that the temperature of the reaction solution did not exceed 60 ° C. At this time, the following tetracarboxylic dianhydride attached to the reaction vessel wall was replaced with N, N-dimethylacetamide 5
It was added while washing with 0 g.
【００５５】[0055]
【化１５】 Embedded image
【００５６】この後、室温で６時間撹拌した後、自然冷
却し、室温まで下がったところで撹拌を止め、ヒドロキ
シ基含有ポリアミド酸ワニス（Ａ）を得た。After stirring at room temperature for 6 hours, the mixture was naturally cooled. When the temperature dropped to room temperature, the stirring was stopped to obtain a hydroxy group-containing polyamic acid varnish (A).
【００５７】次に、このワニスをポアサイズ２μｍのテ
フロン（登録商標）フィルタを用い加圧濾過して異物を
除き、６×６ｃｍのアルミ基板上にスピン塗布した。次
いで、ホットプレート（（株）大日本スクリーン製ＳＫ
Ｗ−６３６）を用いて、１２０℃で４分プリベークし
た。さらにオーブン（（株）光洋リンドバーグ製イナー
トオーブン）を用いて、２００℃３０分、さらに３５０
℃６０分熱処理によりイミド化及びベンゾオキサゾール
化し、厚さ３．７μｍのポリベンゾオキサゾール−ポリ
イミド膜を形成した。Next, the varnish was subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 2 μm to remove foreign substances, and spin-coated on a 6 × 6 cm aluminum substrate. Then, SK made by Hot Plate (Dainippon Screen)
W-636) at 120 ° C. for 4 minutes. Further, using an oven (an inert oven manufactured by Koyo Lindberg Co., Ltd.), 200 ° C. for 30 minutes, and 350 ° C.
By imidization and benzoxazole by heat treatment at 60 ° C. for 60 minutes, a 3.7 μm-thick polybenzoxazole-polyimide film was formed.
【００５８】その後、アルミ基板状に形成したポリベン
ゾオキサゾール−ポリイミド膜上にマスク蒸着により上
部アルミ電極を形成し、該膜の一部をカッタナイフによ
り削り、下部アルミ電極を露出させ、誘電率測定用試料
を作製した。Thereafter, an upper aluminum electrode is formed on the polybenzoxazole-polyimide film formed on the aluminum substrate by mask vapor deposition, a part of the film is shaved with a cutter knife, the lower aluminum electrode is exposed, and the dielectric constant is measured. A sample for use was prepared.
【００５９】この試料を用い、ポリベンゾオキサゾール
−ポリイミド膜の静電容量を測定し、比誘電率を算出し
た。また、静電容量測定用フィルムと同様にして、シリ
コンウエハ上に熱硬化して成膜したポリベンゾオキサゾ
ール−ポリイミド膜を用い、赤外吸収スペクトル（Ｉ
Ｒ）、屈折率（ＴＥ）を測定した。その後、５％重量減
少温度（Ｔｄ５）を測定した。Using this sample, the capacitance of the polybenzoxazole-polyimide film was measured, and the relative dielectric constant was calculated. Further, in the same manner as the capacitance measurement film, a polybenzoxazole-polyimide film formed by heat curing on a silicon wafer was used, and an infrared absorption spectrum (I
R) and the refractive index (TE) were measured. Thereafter, the 5% weight loss temperature (Td5) was measured.
【００６０】赤外吸収スペクトル：ブロード吸収３４０
０ｃｍ-1（ＯＨ） イミド特性吸収１７８９、１７２８ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: broad absorption 340
0 cm -1 (OH) imide characteristic absorption 1789, 1728 cm -1 (CO) benzoxazole characteristic absorption 1481 cm -1 (CO).
【００６１】実施例２ ヒドロキシ基含有ポリアミド酸ワニス（Ａ）を実施例１
と同様にして加圧濾過し、プリベークまで同様に行っ
た。さらに実施例１と同じオーブンを用いて、２００℃
３０分、さらに４００℃２４０分熱処理によりイミド化
及びベンゾオキサゾール化し、厚さ４．１２μｍのポリ
ベンゾオキサゾール−ポリイミド膜を形成した。Example 2 A hydroxy group-containing polyamic acid varnish (A) was prepared in Example 1.
Filtration under pressure was performed in the same manner as described above, and the same procedure was performed up to prebaking. Further, using the same oven as in Example 1, 200 ° C.
Imidation and benzoxazole formation were performed by heat treatment at 400 ° C. for 240 minutes, and a polybenzoxazole-polyimide film having a thickness of 4.12 μm was formed.
【００６２】その後、実施例１と同様にして、誘電率測
定（静電容量測定）用試料を作製し、実施例と同様にし
て、各項目について評価を行った。Thereafter, a sample for dielectric constant measurement (capacitance measurement) was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example.
【００６３】赤外吸収スペクトル：ブロード吸収３５０
０ｃｍ-1（ＯＨ） イミド特性吸収１７９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: broad absorption 350
0 cm -1 (OH) imide characteristic absorption 1793, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【００６４】実施例３ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したＮ，Ｎ−ジメチルアセトアミドを
１５０ｇ入れ、下記（ｃ）式で表される芳香族ジアミン
３１．５２ｇ（７０．０ｍｍｏｌ）を加え完全に溶解し
た。Example 3 A stirring vessel equipped with a blade, a cooling pipe, and a N 2 gas introducing pipe were attached to a 500 ml four-necked flask as a reaction vessel, and then dry N 2 gas was flowed. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled N, N-dimethylacetamide was added, and 31.52 g (70.0 mmol) of an aromatic diamine represented by the following formula (c) was added and completely dissolved.
【００６５】[0065]
【化１６】 Embedded image
【００６６】この後、フラスコをウオーターバスにつ
け、上記（ｂ）式で表されるテトラカルボン酸二無水物
３４．０１ｇ（７６．５５ｍｍｏｌ）を反応液の温度が
６０℃以上にならないよう少量ずつ加えた。この際、反
応容器壁についた下記テトラカルボン酸二無水物をＮ，
Ｎ−ジメチルアセトアミド５０ｇで洗い流しながら加え
た。Thereafter, the flask was placed in a water bath, and 34.01 g (76.55 mmol) of tetracarboxylic dianhydride represented by the above formula (b) was added little by little so that the temperature of the reaction solution did not reach 60 ° C. or more. Was. At this time, the following tetracarboxylic dianhydride attached to the reaction vessel wall was replaced with N,
It was added while washing with 50 g of N-dimethylacetamide.
【００６７】この後、室温で６時間撹拌した後、自然冷
却し、室温まで下がったところで撹拌を止め、ポリアミ
ド酸ワニス（Ｂ）を得た。Then, after stirring at room temperature for 6 hours, the mixture was naturally cooled, and when the temperature dropped to room temperature, the stirring was stopped to obtain a polyamide acid varnish (B).
【００６８】次に、ワニス（Ｂ）を実施例１と同様に加
圧濾過、プリベークを行い、さらに実施例１と同じオー
ブンを用いて、２００℃３０分、さらに４５０℃１２０
分熱処理によりイミド化及びベンザオキサゾール化し、
厚さ４．０μｍのポリベンゾオキサゾール−ポリイミド
膜を形成した。その後、実施例１と同様にして、評価を
行った。 赤外吸収スペクトル：イミド特性吸収１７９３、１７３
５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Next, the varnish (B) was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further, using the same oven as in Example 1, at 200 ° C. for 30 minutes and further at 450 ° C. for 120 minutes.
Imidation and benzoxazole by heat treatment
A 4.0 μm thick polybenzoxazole-polyimide film was formed. Thereafter, evaluation was performed in the same manner as in Example 1. Infrared absorption spectrum: imide characteristic absorption 1793, 173
5 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【００６９】実施例４ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したＮ−メチルピロリドンを１５０ｇ
入れ、下記（ｄ）式で表される芳香族ジアミン（（株）
和歌山精化工業製）１０．８１ｇ（５０．０ｍｍｏｌ）
を加え完全に溶解した。Example 4 A 500 ml four-necked flask as a reaction vessel was equipped with a stirring rod with a blade, a cooling tube, and a N 2 gas introduction tube, and then dried N 2 gas was flowed. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled N-methylpyrrolidone was added.
And an aromatic diamine represented by the following formula (d)
10.81 g (50.0 mmol) manufactured by Wakayama Seika Kogyo
And completely dissolved.
【００７０】[0070]
【化１７】 Embedded image
【００７１】この後、フラスコをウオーターバスにつ
け、ジアミンと等モル量の上記（ｂ）式で表されるテト
ラカルボン酸二無水物２２．２１ｇ（５０．０ｍｍｏ
ｌ）を反応液の温度が６０℃以上にならないよう少量ず
つ加えた。この際、反応容器壁についた上記テトラカル
ボン酸二無水物をＮ−メチルピロリドン５０ｇで洗い流
しながら加えた。この後、室温で６時間撹拌した後、自
然冷却し、室温まで下がったところで撹拌を止め、ヒド
ロキシ基含有ポリアミド酸ワニス（Ｃ）を得た。Thereafter, the flask was placed in a water bath, and an equimolar amount of diamine (22.21 g, 50.0 mmol) of tetracarboxylic dianhydride represented by the above formula (b) was added.
l) was added little by little so that the temperature of the reaction solution did not exceed 60 ° C. At this time, the above tetracarboxylic dianhydride attached to the reaction vessel wall was added while washing with 50 g of N-methylpyrrolidone. Then, after stirring at room temperature for 6 hours, the mixture was naturally cooled. When the temperature dropped to room temperature, the stirring was stopped to obtain a hydroxy group-containing polyamic acid varnish (C).
【００７２】次に、ワニス（Ｃ）を実施例１と同様に加
圧濾過、プリベークを行い、さらに実施例１と同じオー
ブンを用いて、２００℃３０分、さらに４５０℃１２０
分熱処理によりイミド化及びベンザオキサゾール化し、
厚さ３．８μｍのポリベンゾオキサゾール−ポリイミド
膜を形成した。その後、実施例１と同様にして、評価を
行った。Next, the varnish (C) was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further, using the same oven as in Example 1, at 200 ° C. for 30 minutes, and further at 450 ° C. for 120 minutes.
Imidation and benzoxazole by heat treatment
A 3.8 μm-thick polybenzoxazole-polyimide film was formed. Thereafter, evaluation was performed in the same manner as in Example 1.
【００７３】赤外吸収スペクトル：イミド特性吸収１７
９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ） 実施例５ ヒドロキシ基含有ポリアミド酸ワニス（Ｃ）を実施例４
と同様にして加圧濾過、プリベークし、同じオーブンを
用いて、２００℃３０分、さらに５００℃６０分熱処理
によりイミド化及びベンゾオキサゾール化し、厚さ４．
０μｍのポリベンゾオキサゾール−ポリイミド膜を形成
した。Infrared absorption spectrum: imide characteristic absorption 17
93, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO) Example 5 A hydroxy group-containing polyamic acid varnish (C) was used in Example 4.
Filtration under pressure and pre-baking in the same manner as described above, and using the same oven, heat treatment at 200 ° C. for 30 minutes and further at 500 ° C. for 60 minutes to imidize and benzoxazole to obtain a thickness of 3.
A 0 μm polybenzoxazole-polyimide film was formed.
【００７４】その後、実施例１と同様にして、誘電率測
定用試料を作製し、実施例１と同様にして、各項目につ
いて評価を行った。Thereafter, a sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1.
【００７５】赤外吸収スペクトル： イミド特性吸収１
７９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: imide characteristic absorption 1
793, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【００７６】実施例６ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したＮ−メチルピロリドンを１５０ｇ
入れ、下記（ｅ）式で表される芳香族ジアミン（（株）
和歌山精化工業製）１２．４６ｇ（５１．０ｍｍｏｌ）
を加え完全に溶解した。Example 6 A 500 mL four-necked flask as a reaction vessel was equipped with a stirring rod with blades, a cooling pipe, and a N 2 gas introduction pipe, and then dried N 2 gas was flowed. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled N-methylpyrrolidone was added.
And an aromatic diamine represented by the following formula (e) (Co., Ltd.)
12.46 g (51.0 mmol) manufactured by Wakayama Seika Kogyo
And completely dissolved.
【００７７】[0077]
【化１８】 Embedded image
【００７８】この後、フラスコをウオーターバスにつ
け、上記（ｂ）式で表されるテトラカルボン酸二無水物
２２．２１ｇ（５０．０ｍｍｏｌ）を反応液の温度が６
０℃以上にならないよう少量ずつ加えた。この際、反応
容器壁についた上記テトラカルボン酸二無水物をＮ−メ
チルピロリドン５０ｇで洗い流しながら加えた。この
後、室温で６時間撹拌した後、自然冷却し、室温まで下
がったところで撹拌を止め、ポリアミド酸ワニス（Ｄ）
を得た。Then, the flask was placed in a water bath, and 22.21 g (50.0 mmol) of the tetracarboxylic dianhydride represented by the above formula (b) was added to the reaction solution at a temperature of 6 ° C.
It was added little by little so as not to reach 0 ° C or more. At this time, the above tetracarboxylic dianhydride attached to the reaction vessel wall was added while washing with 50 g of N-methylpyrrolidone. Then, after stirring at room temperature for 6 hours, the mixture is naturally cooled, and when the temperature has dropped to room temperature, the stirring is stopped.
I got
【００７９】次に、ワニス（Ｄ）を実施例１と同様に加
圧濾過、プリベークを行い、さらに実施例１と同じオー
ブンを用いて、２００℃３０分、さらに４５０℃１２０
分熱処理によりイミド化及びベンザオキサゾール化し、
厚さ４．１１μｍのポリベンゾオキサゾール−ポリイミ
ド膜を形成した。その後、実施例１と同様にして、各種
評価を行った。Next, the varnish (D) was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further, using the same oven as in Example 1, at 200 ° C. for 30 minutes and further at 450 ° C. for 120 minutes.
Imidation and benzoxazole by heat treatment
A 4.11 μm-thick polybenzoxazole-polyimide film was formed. After that, various evaluations were performed in the same manner as in Example 1.
【００８０】赤外吸収スペクトル： イミド特性吸収１
７９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: imide characteristic absorption 1
793, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【００８１】実施例７ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したγーブチロラクトンを１５０ｇ入
れ、上記（ａ）式で表される芳香族ジアミン１４．６５
ｇ（４０．０ｍｍｏｌ）を加え完全に溶解した。Example 7 A 500 ml four-necked flask as a reaction vessel was equipped with a stirring rod with blades, a cooling tube, and a N 2 gas introduction tube, and then dried N 2 gas was flowed. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled γ-butyrolactone was added, and 14.65 of the aromatic diamine represented by the above formula (a) was added.
g (40.0 mmol) was added and completely dissolved.
【００８２】この後、フラスコをウオーターバスにつ
け、下記（ｆ）式で表されるテトラカルボン酸二無水物
（（株）三菱化学製）１０．５９ｇ（３６．０ｍｍｏ
ｌ）を反応液の温度が６０℃以上にならないよう少量ず
つ加えた。この際、反応容器壁についた下記テトラカル
ボン酸二無水物をγーブチロラクトン５０ｇで洗い流し
ながら加えた。Thereafter, the flask was placed in a water bath, and 10.59 g (36.0 mmol) of tetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation) represented by the following formula (f) was obtained.
l) was added little by little so that the temperature of the reaction solution did not exceed 60 ° C. At this time, the following tetracarboxylic dianhydride attached to the reaction vessel wall was added while washing with 50 g of γ-butyrolactone.
【００８３】[0083]
【化１９】 Embedded image
【００８４】この後、室温で６時間撹拌した後、自然冷
却し、室温まで下がったところで撹拌を止め、ヒドロキ
シ基含有ポリアミド酸ワニス（Ｅ）を得た。Thereafter, the mixture was stirred at room temperature for 6 hours, then cooled naturally, and when the temperature dropped to room temperature, the stirring was stopped to obtain a hydroxy group-containing polyamic acid varnish (E).
【００８５】次に、このワニスを実施例１と同様に加圧
濾過、プリベークを行い、さらに実施例１と同じオーブ
ンを用いて、２００℃３０分、さらに４５０℃１２０分
熱処理によりイミド化及びベンゾオキサゾール化し、厚
さ３．９μｍのポリベンゾオキサゾール−ポリイミド膜
を形成した。その後、実施例１と同様にして、誘電率測
定用試料を作製し、実施例１と同様にして、各項目につ
いて評価を行った。 赤外吸収スペクトル： イミド特性吸収１７９３、１７
３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Next, this varnish was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further subjected to heat treatment at 200 ° C. for 30 minutes and at 450 ° C. for 120 minutes in the same oven as in Example 1 to imidize and benzoate. Oxazole was formed to form a 3.9 μm thick polybenzoxazole-polyimide film. Thereafter, a sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1. Infrared absorption spectrum: imide characteristic absorption 1793, 17
35 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【００８６】実施例８ ヒドロキシ基含有ポリアミド酸ワニス（Ｅ）を実施例７
と同様にして加圧濾過、プリベークし、さらに、実施例
１と同じオーブンを用いて、２００℃３０分、さらに５
００℃１２０分熱処理によりイミド化及びベンゾオキサ
ゾール化し、厚さ４．０μｍのポリベンゾオキサゾール
−ポリイミド膜を形成した。その後、実施例１と同様に
して、誘電率測定用試料を作製し、実施例１と同様にし
て、各項目について評価を行った。 赤外吸収スペクトル： イミド特性吸収１７９３、１７
３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Example 8 A hydroxy group-containing polyamic acid varnish (E) was used in Example 7.
Pressure filtration and pre-baking in the same manner as described above, and further using the same oven as in Example 1 at 200 ° C. for 30 minutes, and further for 5 minutes
By imidization and benzoxazole by heat treatment at 00 ° C. for 120 minutes, a polybenzoxazole-polyimide film having a thickness of 4.0 μm was formed. Thereafter, a sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1. Infrared absorption spectrum: imide characteristic absorption 1793, 17
35 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【００８７】実施例９ 実施例１において、芳香族ジアミン及びテトラカルボン
酸二無水物を加えるまで、実施例１と同様に行い、その
後、５０℃で６時間撹拌した後、無水酢酸１５．６３ｇ
（１５３．１ｍｍｏｌ）、ピリジン１２．１ｇ（１５
３．１ｍｍｏｌ）を添加し、５０℃で３時間攪拌を続け
た。反応後、ポリマーを純水に沈殿させ、８０℃で一晩
乾燥し、ポリマー粉体５４ｇ得た。続いて、このポリマ
ー粉体１０ｇをはかり、ここにＮ，Ｎ−ジメチルアセト
アミド３０ｇを加え５０℃で３時攪拌し、ポリマー粉体
が溶解した後、自然冷却し、室温まで下がったところで
撹拌を止め、ヒドロキシ基含有ポリイミドワニス（Ｆ）
を得た。Example 9 The procedure of Example 1 was repeated, except that the aromatic diamine and the tetracarboxylic dianhydride were added. After stirring at 50 ° C. for 6 hours, 15.63 g of acetic anhydride was added.
(153.1 mmol), 12.1 g of pyridine (15
3.1 mmol) was added and stirring was continued at 50 ° C. for 3 hours. After the reaction, the polymer was precipitated in pure water and dried at 80 ° C. overnight to obtain 54 g of a polymer powder. Subsequently, 10 g of the polymer powder was weighed, 30 g of N, N-dimethylacetamide was added thereto, and the mixture was stirred at 50 ° C. for 3 hours. After the polymer powder was dissolved, the mixture was naturally cooled, and the stirring was stopped when the temperature dropped to room temperature. , Hydroxy group-containing polyimide varnish (F)
I got
【００８８】次にヒドロキシ基含有ポリイミドワニス
（Ｆ）を実施例１と同様にして加圧濾過し、プリベーク
まで同様に行った。さらに実施例１と同じオーブンを用
いて、３５０℃３６０分熱処理によりベンゾオキサゾー
ル化し、厚さ３．９μｍのポリベンゾオキサゾール−ポ
リイミド膜を形成した。その後、実施例１と同様にし
て、誘電率測定（静電容量測定）用試料を作製し、実施
例１と同様にして、各項目について評価を行った。Next, the hydroxy group-containing polyimide varnish (F) was subjected to pressure filtration in the same manner as in Example 1, and the same procedure was repeated until prebaking. Furthermore, using the same oven as in Example 1, benzoxazole was formed by heat treatment at 350 ° C. for 360 minutes to form a 3.9 μm-thick polybenzoxazole-polyimide film. Thereafter, a sample for dielectric constant measurement (capacitance measurement) was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1.
【００８９】赤外吸収スペクトル：ブロード吸収３４０
０ｃｍ-1（ＯＨ） イミド特性吸収１７８９、１７２８ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: broad absorption 340
0 cm -1 (OH) imide characteristic absorption 1789, 1728 cm -1 (CO) benzoxazole characteristic absorption 1481 cm -1 (CO).
【００９０】実施例１０ ヒドロキシ基含有ポリイミドワニス（Ｆ）を実施例１と
同様にして加圧濾過し、プリベークまで同様に行った。
さらに実施例１と同じオーブンを用いて、４００℃２４
０分熱処理によりベンゾオキサゾール化し、厚さ４．０
５μｍのポリベンゾオキサゾール−ポリイミド膜を形成
した。その後、実施例１と同様にして、誘電率測定（静
電容量測定）用試料を作製し、実施例１と同様にして、
各項目について評価を行った。Example 10 The hydroxy group-containing polyimide varnish (F) was subjected to pressure filtration in the same manner as in Example 1, and the same procedure was repeated until prebaking.
Further, using the same oven as in Example 1, 400 ° C.
Benzoxazole by heat treatment for 0 minutes, thickness 4.0
A 5 μm polybenzoxazole-polyimide film was formed. After that, a sample for permittivity measurement (capacitance measurement) was prepared in the same manner as in Example 1, and as in Example 1,
Each item was evaluated.
【００９１】赤外吸収スペクトル：ブロード吸収３５０
０ｃｍ-1（ＯＨ） イミド特性吸収１７９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: broad absorption 350
0 cm -1 (OH) imide characteristic absorption 1793, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【００９２】実施例１１ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したＮ，Ｎ−ジメチルアセトアミドを
１５０ｇ入れ、下記（ｇ）式で表される芳香族ジアミン
２９．５７ｇ（７０ｍｍｏｌ）を加え完全に溶解した。Example 11 A 500 mL four-necked flask as a reaction vessel was equipped with a stirring rod with a blade, a cooling pipe, and a N 2 gas introduction pipe, and then dried N 2 gas was flown. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled N, N-dimethylacetamide was added, and 29.57 g (70 mmol) of an aromatic diamine represented by the following formula (g) was added and completely dissolved.
【００９３】[0093]
【化２０】 Embedded image
【００９４】この後、フラスコをウオーターバスにつ
け、上記（ｂ）式で表されるテトラカルボン酸二無水物
３１．１ｇ（７０ｍｍｏｌ）を反応液の温度が６０℃以
上にならないよう少量ずつ加えた。この際、反応容器壁
についた下記テトラカルボン酸二無水物をＮ，Ｎ−ジメ
チルアセトアミド５０ｇで洗い流しながら加えた。Thereafter, the flask was placed in a water bath, and 31.1 g (70 mmol) of tetracarboxylic dianhydride represented by the above formula (b) was added little by little so that the temperature of the reaction solution did not reach 60 ° C. or higher. At this time, the following tetracarboxylic dianhydride attached to the reaction vessel wall was added while washing with 50 g of N, N-dimethylacetamide.
【００９５】この後、５０℃で６時間撹拌した後、無水
酢酸１５．６３ｇ（１５３．１ｍｍｏｌ）、ピリジン１
２．１ｇ（１５３．１ｍｍｏｌ）を添加し、５０℃で３
時間攪拌を続けた。反応後、ポリマーを純水に沈殿さ
せ、８０℃で一晩乾燥し、ポリマー粉体５２ｇ得た。続
いて、このポリマー粉体１０ｇをはかり、ここにＮ，Ｎ
−ジメチルアセトアミド３０ｇを加え５０℃で３時攪拌
し、ポリマー粉体が溶解した後、自然冷却し、室温まで
下がったところで撹拌を止め、ポリイミドワニス（Ｇ）
を得た。After stirring at 50 ° C. for 6 hours, 15.63 g (153.1 mmol) of acetic anhydride and pyridine 1
2.1 g (153.1 mmol) are added and at 50 ° C. 3
Stirring was continued for hours. After the reaction, the polymer was precipitated in pure water and dried at 80 ° C. overnight to obtain 52 g of a polymer powder. Subsequently, 10 g of the polymer powder was weighed, and N, N
-Add 30 g of dimethylacetamide, stir at 50 ° C. for 3 hours, allow the polymer powder to dissolve, allow to cool naturally, stop stirring when the temperature has dropped to room temperature, and apply polyimide varnish (G).
I got
【００９６】次に、ワニス（Ｇ）を実施例１と同様に加
圧濾過、プリベークを行い、さらに実施例１と同じオー
ブンを用いて、さらに４５０℃１２０分熱処理によりベ
ンザオキサゾール化し、厚さ３．８５μｍのポリベンゾ
オキサゾール−ポリイミド膜を形成した。その後、実施
例１と同様にして、評価を行った。Next, the varnish (G) was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further subjected to heat treatment at 450.degree. A 0.85 μm polybenzoxazole-polyimide film was formed. Thereafter, evaluation was performed in the same manner as in Example 1.
【００９７】赤外吸収スペクトル：イミド特性吸収１７
９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: imide characteristic absorption 17
93, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【００９８】実施例１２ 実施例４において、実施例４と同じ芳香族ジアミンとテ
トラカルボン酸二無水物を用い、実施例４と同様にＮ−
メチルピロリドン５０ｇに溶解した。この後、５０℃で
３時間撹拌した後、トルエン５０ｇを添加し、反応生成
水をトルエン共沸によって脱水しながら、１２０℃で３
時間反応した。その後、１６０℃まで反応液の温度を上
げドルエンを留去し、自然冷却、室温まで下がったとこ
ろで撹拌を止め、ヒドロキシ基含有ポリイミドワニス
（Ｈ）を得た。Example 12 In Example 4, the same aromatic diamine and tetracarboxylic dianhydride were used as in Example 4, and N-
It was dissolved in 50 g of methylpyrrolidone. Then, after stirring at 50 ° C. for 3 hours, 50 g of toluene was added, and the reaction product was dehydrated by azeotropic distillation with toluene at 120 ° C. for 3 hours.
Reacted for hours. Thereafter, the temperature of the reaction solution was raised to 160 ° C., and dolene was distilled off. After cooling naturally, when the temperature dropped to room temperature, stirring was stopped to obtain a hydroxy group-containing polyimide varnish (H).
【００９９】次に、ワニス（Ｈ）を実施例１と同様に加
圧濾過、プリベークを行い、さらに実施例１と同じオー
ブンを用いて、さらに４５０℃１２０分熱処理によりベ
ンザオキサゾール化し、厚さ３．７５μｍのポリベンゾ
オキサゾール−ポリイミド膜を形成した。その後、実施
例１と同様にして、評価を行った。Next, the varnish (H) was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further subjected to heat treatment at 450 ° C. for 120 minutes in the same oven as in Example 1 to form a benzoxazole, and a thickness of 3%. A 0.75 μm polybenzoxazole-polyimide film was formed. Thereafter, evaluation was performed in the same manner as in Example 1.
【０１００】赤外吸収スペクトル：ブロード吸収３５０
０ｃｍ-1（ＯＨ） イミド特性吸収１７９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: broad absorption 350
0 cm -1 (OH) imide characteristic absorption 1793, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【０１０１】実施例１３ ヒドロキシ基含有ポリイミドワニス（Ｈ）を実施例１と
同様にして加圧濾過、プリベークし、同じオーブンを用
いて、５００℃６０分熱処理によりベンゾオキサゾール
化し、厚さ４．２２μｍのポリベンゾオキサゾール−ポ
リイミド膜を形成した。その後、実施例１と同様にし
て、誘電率測定用試料を作製し、実施例１と同様にし
て、各項目について評価を行った。Example 13 The hydroxy group-containing polyimide varnish (H) was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and benzoxazole was formed by heat treatment at 500 ° C. for 60 minutes in the same oven to obtain a 4.22 μm thick film. Of a polybenzoxazole-polyimide film was formed. Thereafter, a sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1.
【０１０２】赤外吸収スペクトル：イミド特性吸収１７
９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: imide characteristic absorption 17
93, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【０１０３】実施例１４ 実施例５において、実施例５と同じ芳香族ジアミンとテ
トラカルボン酸二無水物を用い、実施例５と同様にＮ−
メチルピロリドン５０ｇに溶解した。この後、５０℃で
３時間撹拌した後、トルエン５０ｇを添加し、反応生成
水をトルエン共沸によって脱水しながら、１２０℃で３
時間反応した。その後、１６０℃まで反応液の温度を上
げドルエンを留去し、自然冷却、室温まで下がったとこ
ろで撹拌を止め、ポリイミドワニス（Ｉ）を得た。Example 14 In Example 5, the same aromatic diamine and tetracarboxylic dianhydride as in Example 5 were used, and N-
It was dissolved in 50 g of methylpyrrolidone. Then, after stirring at 50 ° C. for 3 hours, 50 g of toluene was added, and the reaction product was dehydrated by azeotropic distillation with toluene at 120 ° C. for 3 hours.
Reacted for hours. Thereafter, the temperature of the reaction solution was raised to 160 ° C., and dolene was distilled off. After cooling naturally, when the temperature dropped to room temperature, stirring was stopped to obtain a polyimide varnish (I).
【０１０４】次に、ワニス（Ｉ）を実施例１と同様に加
圧濾過、プリベークを行い、さらに実施例１と同じオー
ブンを用いて、さらに４５０℃１２０分熱処理によりベ
ンザオキサゾール化し、厚さ３．９５μｍのポリベンゾ
オキサゾール−ポリイミド膜を形成した。その後、実施
例１と同様にして、評価を行った。Next, the varnish (I) was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further subjected to heat treatment at 450 ° C. for 120 minutes in the same oven as in Example 1 to form a benzoxazole, and a thickness of 3%. A .95 μm polybenzoxazole-polyimide film was formed. Thereafter, evaluation was performed in the same manner as in Example 1.
【０１０５】赤外吸収スペクトル：イミド特性吸収１７
９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: imide characteristic absorption 17
93, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【０１０６】実施例１５ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したγーブチロラクトンを１５０ｇ入
れ、上記（ａ）式で表される芳香族ジアミン１４．６５
ｇ（４０ｍｍｏｌ）を加え完全に溶解した。Example 15 A stirring vessel with a blade, a cooling pipe, and a N 2 gas introducing pipe were attached to a 500 ml four-necked flask as a reaction vessel, and then dry N 2 gas was flowed. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled γ-butyrolactone is added, and the aromatic diamine represented by the above formula (a) 14.65.
g (40 mmol) was added and completely dissolved.
【０１０７】この後、フラスコをウオーターバスにつ
け、上記（ｆ）式で表されるテトラカルボン酸二無水物
９．４２ｇ（３２ｍｍｏｌ）を反応液の温度が６０℃以
上にならないよう少量ずつ加えた。この際、反応容器壁
についた下記テトラカルボン酸二無水物をγーブチロラ
クトン５０ｇで洗い流しながら加えた。Thereafter, the flask was placed in a water bath, and 9.42 g (32 mmol) of tetracarboxylic dianhydride represented by the above formula (f) was added little by little so that the temperature of the reaction solution did not reach 60 ° C. or higher. At this time, the following tetracarboxylic dianhydride attached to the reaction vessel wall was added while washing with 50 g of γ-butyrolactone.
【０１０８】この後、６０℃で２時間撹拌した後、下記
（ｈ）式で表される末端封止剤（（株）東京化成工業
製）を２．３６ｇ（１６ｍｍｏｌ）を添加した。この
際、反応容器壁についた下記末端封止剤をγーブチロラ
クトン５ｇで洗い流しながら加えた。After stirring at 60 ° C. for 2 hours, 2.36 g (16 mmol) of a terminal blocking agent represented by the following formula (h) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. At this time, the following terminal blocking agent attached to the reaction vessel wall was added while washing with 5 g of γ-butyrolactone.
【０１０９】[0109]
【化２１】 Embedded image
【０１１０】この後、５０℃で２時間撹拌した後、無水
酢酸８．１７ｇ（８０ｍｍｏｌ）、ピリジン６．３２ｇ
（８０ｍｍｏｌ）を添加し、５０℃で３時間攪拌を続け
た。反応後、ポリマーを純水に沈殿させ、８０℃で一晩
乾燥し、ポリマー粉体２３．０ｇ得た。続いて、このポ
リマー粉体１０．０ｇをはかり、ここにγーブチロラク
トン３０ｇを加え５０℃で３時間攪拌し、ポリマー粉体
が溶解した後、自然冷却し、室温まで下がったところで
撹拌を止め、ヒドロキシ基含有ポリイミド（Ｊ）を得
た。After stirring at 50 ° C. for 2 hours, 8.17 g (80 mmol) of acetic anhydride and 6.32 g of pyridine were obtained.
(80 mmol) was added and stirring was continued at 50 ° C. for 3 hours. After the reaction, the polymer was precipitated in pure water and dried at 80 ° C. overnight to obtain 23.0 g of a polymer powder. Subsequently, 10.0 g of the polymer powder was weighed, 30 g of γ-butyrolactone was added thereto, and the mixture was stirred at 50 ° C. for 3 hours. After the polymer powder was dissolved, the mixture was naturally cooled, and the stirring was stopped when the temperature dropped to room temperature. Thus, a hydroxy group-containing polyimide (J) was obtained.
【０１１１】次に、このワニスを実施例１と同様に加圧
濾過、プリベークを行い、さらに実施例１と同じオーブ
ンを用いて、４５０℃１２０分熱処理によりベンゾオキ
サゾール化し、厚さ４．２５μｍのポリベンゾオキサゾ
ール−ポリイミド膜を形成した。その後、実施例１と同
様にして、誘電率測定用試料を作製し、実施例１と同様
にして、各項目について評価を行った。Next, this varnish was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further subjected to heat treatment at 450 ° C. for 120 minutes in the same oven as in Example 1 to form a benzoxazole, thereby obtaining a 4.25 μm-thick varnish. A polybenzoxazole-polyimide film was formed. Thereafter, a sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1.
【０１１２】赤外吸収スペクトル：イミド特性吸収１７
９３、１７３５ｃｍ-1（ＣＯ） ベンゾオキサゾール特性吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: imide characteristic absorption 17
93, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【０１１３】実施例１６ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したＮ−メチルピロリドンを１５０ｇ
入れ、上記（ｅ）式で表される芳香族ジアミン９．７７
ｇ（４０ｍｍｏｌ）を加え完全に溶解した。Example 16 A stirring vessel equipped with a blade, a cooling pipe, and a N 2 gas introducing pipe were attached to a 500 ml four-necked flask as a reaction vessel, and then dry N 2 gas was flowed. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled N-methylpyrrolidone was added.
9.77 of the aromatic diamine represented by the above formula (e)
g (40 mmol) was added and completely dissolved.
【０１１４】この後、フラスコをウオーターバスにつ
け、上記（ｂ）式で表されるテトラカルボン酸二無水物
２２．２１ｇ（５０ｍｍｏｌ）を反応液の温度が６０℃
以上にならないよう少量ずつ加えた。この際、反応容器
壁についた上記テトラカルボン酸二無水物をＮ−メチル
ピロリドン５０ｇで洗い流しながら加えた。この後、５
０℃で２時間撹拌した後、下記（ｉ）式で表される末端
封止剤（（株）富士フイルム製）を２．３４ｇ（２０ｍ
ｍｏｌ）を添加した。この際、反応容器壁についた下記
末端封止剤をＮ−メチルピロリドン５ｇで洗い流しなが
ら加えた。Thereafter, the flask was placed in a water bath, and 22.21 g (50 mmol) of the tetracarboxylic dianhydride represented by the formula (b) was added to the reaction solution at a temperature of 60 ° C.
It was added little by little so as not to exceed the above. At this time, the above tetracarboxylic dianhydride attached to the reaction vessel wall was added while washing with 50 g of N-methylpyrrolidone. After this, 5
After stirring at 0 ° C. for 2 hours, 2.34 g (20 m) of a terminal blocking agent (manufactured by FUJIFILM Corporation) represented by the following formula (i):
mol) was added. At this time, the following terminal blocking agent attached to the reaction vessel wall was added while washing with 5 g of N-methylpyrrolidone.
【０１１５】[0115]
【化２２】 Embedded image
【０１１６】この後、５０℃で２時間撹拌した後、トル
エン５０ｇを添加し、反応生成水をトルエン共沸によっ
て脱水しながら、１２０℃で３時間反応した。その後、
１５０℃まで反応液の温度を上げドルエンを留去し、自
然冷却、室温まで下がったところで撹拌を止め、ポリイ
ミドワニス（Ｋ）を得た。After stirring at 50 ° C. for 2 hours, 50 g of toluene was added, and the reaction was carried out at 120 ° C. for 3 hours while dehydrating the reaction product water by azeotropic distillation with toluene. afterwards,
The temperature of the reaction solution was raised to 150 ° C., and the dolene was distilled off. After cooling naturally, when the temperature dropped to room temperature, stirring was stopped to obtain a polyimide varnish (K).
【０１１７】次に、ワニス（Ｋ）を実施例１と同様に加
圧濾過、プリベークを行い、さらに実施例１と同じオー
ブンを用いて、５００℃６０分熱処理によりイミド化及
びベンゾオキサゾール化し、厚さ４．２５μｍのポリベ
ンゾオキサゾール−ポリイミド膜を形成した。その後、
実施例１と同様にして、誘電率測定用試料を作製し、実
施例１と同様にして、各項目について評価を行った。Next, the varnish (K) was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further subjected to heat treatment at 500 ° C. for 60 minutes in the same oven as in Example 1 to obtain imidization and benzoxazole, and A polybenzoxazole-polyimide film having a thickness of 4.25 μm was formed. afterwards,
A sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1.
【０１１８】赤外吸収スペクトル：イミド特性吸収１７
９３、１７３５ｃｍ-1（ＣＯ）ベンゾオキサゾール特性
吸収１４８１ｃｍ-1（ＣＯ）。Infrared absorption spectrum: imide characteristic absorption 17
93, 1735 cm -1 (CO) Benzoxazole characteristic absorption 1481 cm -1 (CO).
【０１１９】比較例１ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したＮ，Ｎ−ジメチルアセトアミドを
１５０ｇ入れ、下記（ｊ）式で表される芳香族ジアミン
（（株）和歌山精化工業製）１０．０１ｇ（５０ｍｍｏ
ｌ）を加え完全に溶解した。Comparative Example 1 A 500 mL four-necked flask as a reaction vessel was equipped with a stirring rod with a blade, a cooling pipe, and a N 2 gas introduction pipe, and then dried N 2 gas was flowed. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled N, N-dimethylacetamide was added, and 10.01 g (50 mmo) of an aromatic diamine represented by the following formula (j) (manufactured by Wakayama Seika Kogyo).
l) was added and completely dissolved.
【０１２０】[0120]
【化２３】 Embedded image
【０１２１】この後、フラスコをウオーターバスにつ
け、ジアミンと等モル量の下記（ｋ）式で表されるテト
ラカルボン酸二無水物（（株）ダイセル化学工業製）１
０．９２ｇ（５０ｍｍｏｌ）を反応液の温度が６０℃以
上にならないよう少量ずつ加えた。この際、反応容器壁
についた下記テトラカルボン酸二無水物をＮ，Ｎ−ジメ
チルアセトアミド５０ｇで洗い流しながら加えた。Thereafter, the flask was placed in a water bath, and equimolar amounts of diamine and tetracarboxylic dianhydride represented by the following formula (k) (manufactured by Daicel Chemical Industries, Ltd.) were added.
0.92 g (50 mmol) was added little by little so that the temperature of the reaction solution did not exceed 60 ° C. At this time, the following tetracarboxylic dianhydride attached to the reaction vessel wall was added while washing with 50 g of N, N-dimethylacetamide.
【０１２２】[0122]
【化２４】 Embedded image
【０１２３】この後、室温で６時間撹拌した後、自然冷
却し、室温まで下がったところで撹拌を止め、ポリアミ
ド酸ワニス（Ｌ）を得た。Thereafter, the mixture was stirred at room temperature for 6 hours, then cooled naturally, and when the temperature dropped to room temperature, the stirring was stopped to obtain a polyamic acid varnish (L).
【０１２４】次に、このワニスを実施例１と同様に加圧
濾過、プリベークを行い、さらに実施例１と同じオーブ
ンを用いて、２００℃３０分、さらに３５０℃６０分熱
処理によりイミド化し、厚さ４．１１μｍのポリイミド
膜を形成した。Next, this varnish was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further imidized by heat treatment at 200 ° C. for 30 minutes and then at 350 ° C. for 60 minutes in the same oven as in Example 1. A polyimide film having a thickness of 4.11 μm was formed.
【０１２５】その後、実施例１と同様にして、誘電率測
定用試料を作製し、実施例１と同様にして、各項目につ
いて評価を行った。赤外吸収スペクトルでイミド特性吸
収１７７８、１７２４ｃｍ-1（ＣＯ）を確認した。Thereafter, a sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1. In the infrared absorption spectrum, imide characteristic absorptions of 1778 and 1724 cm -1 (CO) were confirmed.
【０１２６】比較例２ ポリアミド酸ワニス（Ｌ）を比較例１と同様にして加圧
濾過、プリベークを行い、さらに実施例１と同じオーブ
ンを用いて、２００℃３０分、さらに３５０℃６０分熱
処理によりイミド化し、厚さ４．０μｍのポリイミド膜
を形成した。Comparative Example 2 The polyamide acid varnish (L) was subjected to pressure filtration and pre-baking in the same manner as in Comparative Example 1, and then heat-treated at 200 ° C. for 30 minutes and further at 350 ° C. for 60 minutes in the same oven as in Example 1. To form a polyimide film having a thickness of 4.0 μm.
【０１２７】その後、実施例１と同様にして、誘電率測
定用試料を作製し、実施例１と同様にして、各項目につ
いて評価を行った。赤外吸収スペクトルでイミド特性吸
収１７７９、１７２４ｃｍ-1（ＣＯ）を確認した。Thereafter, a sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1. In the infrared absorption spectrum, imide characteristic absorptions of 1779 and 1724 cm -1 (CO) were confirmed.
【０１２８】比較例３ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留しＮ−メチルピロリドンを５０ｇ入
れ、上記（ａ）式で表される芳香族ジアミン１８．３ｇ
（５０ｍｍｏｌ）、グリシジルメチルエーテル２６．４
ｇ（０．３ｍｏｌ）を溶解させ、溶液の温度を−１５℃
まで冷却した。ここにジフェニルエーテルジカルボン酸
ジクロリド７．３８ｇ（２５ｍｍｏｌ）、イソフタル酸
ジクロリド５．０８ｇ（２５ｍｍｏｌ）をガンマブチロ
ラクトン２５ｇに溶解させた溶液を内部の温度が０℃を
越えないように滴下した。滴下終了後、６時間−１５℃
で攪拌を続けた。Comparative Example 3 A stirring vessel equipped with a blade, a cooling pipe, and a N 2 gas introducing pipe were attached to a 500 ml four-necked flask as a reaction vessel, and then dry N 2 gas was flown. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 50 g of N-methylpyrrolidone was added by dehydration distillation, and 18.3 g of the aromatic diamine represented by the above formula (a)
(50 mmol), glycidyl methyl ether 26.4
g (0.3 mol) is dissolved, and the temperature of the solution is set to -15 ° C.
Cooled down. A solution prepared by dissolving 7.38 g (25 mmol) of diphenyl ether dicarboxylic acid dichloride and 5.08 g (25 mmol) of isophthalic acid dichloride in 25 g of gamma-butyrolactone was added dropwise so that the internal temperature did not exceed 0 ° C. After dropping, -15 ° C for 6 hours
And continued stirring.
【０１２９】反応終了後、溶液を水３ｌに投入して白色
の沈殿を集めた。この沈殿をろ過で集めて、水で３回洗
浄した後、８０℃の真空乾燥機で２０時間乾燥した。After completion of the reaction, the solution was poured into 3 l of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours.
【０１３０】この得られたポリベンゾオキサゾール前駆
体を、固形分濃度３０ｗｔ％になるようにＮ−メチルピ
ロリドンを加え溶解させ、ポリベンゾオキサゾール前駆
体ワニス（Ｍ）を得た。The obtained polybenzoxazole precursor was dissolved by adding N-methylpyrrolidone so as to have a solid concentration of 30% by weight to obtain a polybenzoxazole precursor varnish (M).
【０１３１】次に、このワニスを実施例１と同様に加圧
濾過、プリベークを行い、さらに実施例１と同じオーブ
ンを用いて、２００℃３０分、さらに３５０℃６０分熱
処理によりベンゾオキサゾール化し、厚さ４．０２μｍ
のポリベンゾオキサゾール膜を形成した。Next, this varnish was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further subjected to heat treatment at 200 ° C. for 30 minutes and then at 350 ° C. for 60 minutes using the same oven as in Example 1, to form a benzoxazole. 4.02 μm thickness
Was formed.
【０１３２】その後、実施例１と同様にして、誘電率測
定用試料を作製し、実施例１と同様にして、各項目につ
いて評価を行った。赤外吸収スペクトルでベンゾオキサ
ゾール特性吸収１４８６ｃｍ-1（ＣＯ）を確認した。Thereafter, a sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1. Benzoxazole characteristic absorption of 1486 cm -1 (CO) was confirmed by an infrared absorption spectrum.
【０１３３】比較例４ ポリベンゾオキサゾール前駆体ワニス（Ｍ）を比較例３
と同様にして加圧濾過、プリベークを行い、さらに実施
例１と同じオーブンを用いて、２００℃３０分、さらに
５００℃１２０分熱処理によりベンゾオキサゾール化
し、厚さ４．０８μｍのポリベンゾオキサゾール膜を形
成した。Comparative Example 4 A polybenzoxazole precursor varnish (M) was used in Comparative Example 3.
Then, pressure filtration and pre-baking are performed in the same manner as described above, and benzoxazole is formed by heat treatment at 200 ° C. for 30 minutes and then at 500 ° C. for 120 minutes using the same oven as in Example 1 to form a polybenzoxazole film having a thickness of 4.08 μm. Formed.
【０１３４】その後、実施例１と同様にして、誘電率測
定用試料を作製し、実施例１と同様にして、各項目につ
いて評価を行った。赤外吸収スペクトルでベンゾオキサ
ゾール特性吸収１４８６ｃｍ-1（ＣＯ）を確認した。Thereafter, a sample for dielectric constant measurement was prepared in the same manner as in Example 1, and each item was evaluated in the same manner as in Example 1. Benzoxazole characteristic absorption of 1486 cm -1 (CO) was confirmed by an infrared absorption spectrum.
【０１３５】比較例５ 反応容器である５００ｍｌの４つ口フラスコに、羽根付
撹拌棒、冷却管、Ｎ2ガス導入管を取り付けた後、乾燥
Ｎ2ガスを流した。フラスコ内をＮ2ガスで十分置換し、
その後、脱水蒸留したγーブチロラクトンを１５０ｇ入
れ、上記（ｊ）式で表される芳香族ジアミン９．０１ｇ
（４５ｍｍｏｌ）を加え完全に溶解した。Comparative Example 5 A stirring vessel equipped with a blade, a cooling pipe, and a N 2 gas introducing pipe were attached to a 500 ml four-necked flask as a reaction vessel, and then dry N 2 gas was flowed. The inside of the flask is sufficiently replaced with N 2 gas,
Thereafter, 150 g of dehydrated and distilled γ-butyrolactone is added, and 9.01 g of the aromatic diamine represented by the above formula (j) is added.
(45 mmol) was added and completely dissolved.
【０１３６】この後、フラスコをウオーターバスにつ
け、上記（ｋ）式で表されるテトラカルボン酸二無水物
１０．９２ｇ（５０ｍｍｏｌ）を反応液の温度が６０℃
以上にならないよう少量ずつ加えた。この際、反応容器
壁についた下記テトラカルボン酸二無水物をγーブチロ
ラクトン５０ｇで洗い流しながら加えた。Thereafter, the flask was placed in a water bath, and 10.92 g (50 mmol) of the tetracarboxylic dianhydride represented by the above formula (k) was added to the reaction solution at a temperature of 60 ° C.
It was added little by little so as not to exceed the above. At this time, the following tetracarboxylic dianhydride attached to the reaction vessel wall was added while washing with 50 g of γ-butyrolactone.
【０１３７】この後、５０℃で４時間撹拌した後、トル
エン５０ｇを添加し、反応生成水をトルエン共沸によっ
て脱水しながら、１２０℃で３時間反応した。その後、
１５０℃まで反応液の温度を上げドルエンを留去し、自
然冷却、室温まで下がったところで撹拌を止め、ヒドロ
キシ基含有ポリイミドワニス（Ｎ）を得た。Thereafter, after stirring at 50 ° C. for 4 hours, 50 g of toluene was added, and the reaction was carried out at 120 ° C. for 3 hours while dehydrating the reaction product water by azeotropic distillation with toluene. afterwards,
The temperature of the reaction solution was raised to 150 ° C., and dolene was distilled off. After cooling to room temperature, stirring was stopped when the temperature dropped to room temperature, to obtain a hydroxy group-containing polyimide varnish (N).
【０１３８】次に、このワニスを実施例１と同様に加圧
濾過、プリベークを行い、さらに実施例１と同じオーブ
ンを用いて、４００℃２４０分熱処理し、厚さ３．９８
μｍの膜を形成した。その後、実施例１と同様にして、
誘電率測定用試料を作製し、実施例１と同様にして、各
項目について評価を行った。赤外吸収スペクトルでイミ
ド特性吸収１７７８、１７２４ｃｍ-1（ＣＯ）を確認し
た。Next, this varnish was subjected to pressure filtration and pre-baking in the same manner as in Example 1, and further heat-treated at 400 ° C. for 240 minutes in the same oven as in Example 1 to a thickness of 3.98.
A μm film was formed. Then, as in Example 1,
A sample for dielectric constant measurement was prepared, and each item was evaluated in the same manner as in Example 1. In the infrared absorption spectrum, imide characteristic absorptions of 1778 and 1724 cm -1 (CO) were confirmed.
【０１３９】実施例１〜１６、比較例１〜５の測定結果
を表１に示した。実施例１〜３のＩＲスペクトルをそれ
ぞれ図１〜３に、実施例９のＩＲスペクトルを図４、５
に、実施例１０のＩＲスペクトルを図６に、実施例１１
のＩＲスペクトルを図７、８に、実施例１２のＩＲスペ
クトルを図９、１０に示した。Table 1 shows the measurement results of Examples 1 to 16 and Comparative Examples 1 to 5. The IR spectra of Examples 1 to 3 are shown in FIGS. 1 to 3, respectively, and the IR spectra of Example 9 are shown in FIGS.
FIG. 6 shows the IR spectrum of Example 10, and FIG.
7 and 8 are shown in FIGS. 7 and 8, and the IR spectrum of Example 12 is shown in FIGS.
【０１４０】[0140]
【表１】 [Table 1]
【０１４１】[0141]
【発明の効果】本発明によれば、εが低く、かつ高耐熱
なポリベンゾオキサゾール−ポリイミド樹脂が得られる
ため、計算機用薄膜多層基板に代表されるところの、高
速信号処理が求められる基板、または素子の絶縁層に本
材料を用いることができる。According to the present invention, a polybenzoxazole-polyimide resin having a low ε and a high heat resistance can be obtained. Therefore, a substrate requiring high-speed signal processing represented by a thin film multilayer substrate for a computer, Alternatively, the present material can be used for an insulating layer of an element.
【図１】実施例１で得られたポリベンゾオキサゾール−
ポリイミド膜のＩＲスペクトルFIG. 1 shows the polybenzoxazole obtained in Example 1.
IR spectrum of polyimide film
【図２】実施例２で得られたポリベンゾオキサゾール−
ポリイミド膜のＩＲスペクトルFIG. 2 shows the polybenzoxazole obtained in Example 2.
IR spectrum of polyimide film
【図３】実施例３で得られたポリベンゾオキサゾール−
ポリイミド膜のＩＲスペクトルFIG. 3 shows the polybenzoxazole obtained in Example 3.
IR spectrum of polyimide film
【図４】実施例９で得られたポリイミドのＩＲスペクト
ルFIG. 4 is an IR spectrum of the polyimide obtained in Example 9.
【図５】実施例９で得られたポリベンゾオキサゾール−
ポリイミド膜のＩＲスペクトルFIG. 5 shows the polybenzoxazole obtained in Example 9.
IR spectrum of polyimide film
【図６】実施例１０で得られたポリベンゾオキサゾール
−ポリイミド膜のＩＲスペクトルFIG. 6 is an IR spectrum of the polybenzoxazole-polyimide film obtained in Example 10.
【図７】実施例１１で得られたポリイミドのＩＲスペク
トルFIG. 7 is an IR spectrum of the polyimide obtained in Example 11.
【図８】実施例１１で得られたポリベンゾオキサゾール
−ポリイミド膜のＩＲスペクトルFIG. 8 is an IR spectrum of the polybenzoxazole-polyimide film obtained in Example 11.
【図９】実施例１２で得られたポリイミドのＩＲスペク
トルFIG. 9 is an IR spectrum of the polyimide obtained in Example 12.
【図１０】実施例１２で得られたポリベンゾオキサゾー
ル−ポリイミド膜のＩＲスペクトルFIG. 10 is an IR spectrum of the polybenzoxazole-polyimide film obtained in Example 12.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J043 PA02 PA04 PA08 PA19 PC015 PC016 PC036 PC075 PC076 PC085 PC086 PC115 PC116 QB26 RA06 RA34 RA35 RA52 SA06 SA63 SA71 SA72 SB01 SB02 TA22 TB01 TB02 UA121 UA122 UA131 UA132 UB011 UB012 UB021 UB022 UB061 UB062 UB121 UB122 UB161 UB162 UB401 UB402 XA16 XA19 YA06 YA07 ZA12 ZA43 ZB47 ZB50 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J043 PA02 PA04 PA08 PA19 PC015 PC016 PC036 PC075 PC076 PC085 PC086 PC115 PC116 QB26 RA06 RA34 RA35 RA52 SA06 SA63 SA71 SA72 SB01 SB02 TA22 TB01 TB02 UA121 UA122 UA131 UA132 UB011 UB01206 UB021 UB121 UB122 UB161 UB162 UB401 UB402 XA16 XA19 YA06 YA07 ZA12 ZA43 ZB47 ZB50
Claims (5)
位からなることを特徴とするポリアミド酸組成物。 【化１】 （式中、Ｒ１、Ｒ２はメチレン、酸素、C(CH3)2、C(C
F3)2、COOのうちのいずれかの基を示す。Ｒ３は水素原
子、炭素数１から１０までの炭化水素基、（メタ）アク
リロイルオキシエチル基、（メタ）アクリロイルオキシ
ｎ−プロピル基、（メタ）アクリロイルオキシｉ−プロ
ピル基、（メタ）アクリロイルオキシｎ−ブチル基のう
ちのいずれかの基を示す。Ｒ４は水素原子、炭素数１か
ら４までの炭化水素基、炭素数１から４までのアルコキ
シ基、エステル基、カルボキシル基、水酸基を示す。Ｒ
５は水素原子、炭素数１から６までの炭化水素基、Ｒ６
−ＣＯ基、Ｒ６−ＯＣＯ基を示す。Ｒ６は水素原子、炭
素数１から４までの炭化水素基を示す。ｐ、ｑは０から
２までの整数を示す。ｒ、ｓは０または１を示す。）1. A polyamic acid composition comprising a repeating unit represented by the following general formula (1). Embedded image (Wherein R 1 and R 2 are methylene, oxygen, C (CH 3 ) 2 , C (C
F 3 ) 2 represents one of COO groups. R3 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a (meth) acryloyloxyethyl group, a (meth) acryloyloxy n-propyl group, a (meth) acryloyloxy i-propyl group, a (meth) acryloyloxy n Represents any one of -butyl groups. R4 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an ester group, a carboxyl group, or a hydroxyl group. R
5 is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, R6
-CO group and R6-OCO group are shown. R6 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. p and q each represent an integer from 0 to 2. r and s represent 0 or 1. )
位からなることを特徴とするポリアミド酸組成物。 【化２】 （式中、Ｒ１、Ｒ２はメチレン、酸素、C(CH3)2、C(C
F3)2、COOのうちのいずれかの基を示す。Ｒ３は水素原
子、炭素数１から１０までの炭化水素基、（メタ）アク
リロイルオキシエチル基、（メタ）アクリロイルオキシ
ｎ−プロピル基、（メタ）アクリロイルオキシｉ−プロ
ピル基、（メタ）アクリロイルオキシｎ−ブチル基のう
ちのいずれかの基を示す。Ｒ４は水素原子、炭素数１か
ら４までの炭化水素基、炭素数１から４までのアルコキ
シ基、エステル基、カルボキシル基、水酸基を示す。Ｒ
５は水素原子、炭素数１から６までの炭化水素基、Ｒ６
−ＣＯ基、Ｒ６−ＯＣＯ基を示す。Ｒ６は水素原子、炭
素数１から４までの炭化水素基を示す。ｐ、ｑは０から
２までの整数を示す。ｒ、ｓは０または１を示す。）2. A polyamic acid composition comprising a repeating unit represented by the following general formula (2). Embedded image (Wherein R 1 and R 2 are methylene, oxygen, C (CH 3 ) 2 , C (C
F 3 ) 2 represents one of COO groups. R3 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a (meth) acryloyloxyethyl group, a (meth) acryloyloxy n-propyl group, a (meth) acryloyloxy i-propyl group, a (meth) acryloyloxy n Represents any one of -butyl groups. R4 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an ester group, a carboxyl group, or a hydroxyl group. R
5 is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, R6
-CO group and R6-OCO group are shown. R6 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. p and q each represent an integer from 0 to 2. r and s represent 0 or 1. )
位からなることを特徴とする可溶性ポリイミド組成物。 【化３】 （式中、Ｒ１、Ｒ２はメチレン、酸素、C(CH3)2、C(C
F3)2、COOのうちのいずれかの基を示す。Ｒ４は水素原
子、炭素数１から４までの炭化水素基、炭素数１から４
までのアルコキシ基、エステル基、カルボキシル基、水
酸基を示す。Ｒ５は水素原子、炭素数１から６までの炭
化水素基、Ｒ６−ＣＯ基、Ｒ６−ＯＣＯ基を示す。Ｒ６
は炭素数１から４までの炭化水素基を示す。ｐ、ｑは０
から２までの整数を示す。ｒ、ｓは０または１を示
す。）3. A soluble polyimide composition comprising a repeating unit represented by the following general formula (3). Embedded image (Wherein R 1 and R 2 are methylene, oxygen, C (CH 3 ) 2 , C (C
F 3 ) 2 represents one of COO groups. R4 is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
Up to an alkoxy group, an ester group, a carboxyl group, and a hydroxyl group. R5 represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an R6-CO group, or an R6-OCO group. R6
Represents a hydrocarbon group having 1 to 4 carbon atoms. p and q are 0
And an integer from 2 to 2. r and s represent 0 or 1. )
位からなることを特徴とする可溶性ポリイミド組成物。 【化４】 （式中、Ｒ１、Ｒ２はメチレン、酸素、C(CH3)2、C(C
F3)2、COOのうちのいずれかの基を示す。Ｒ４は水素原
子、炭素数１から４までの炭化水素基、炭素数１から４
までのアルコキシ基、エステル基、カルボキシル基、水
酸基を示す。Ｒ５は水素原子、炭素数１から６までの炭
化水素基、Ｒ６−ＣＯ基、Ｒ６−ＯＣＯ基を示す。Ｒ６
は炭素数１から４までの炭化水素基を示す。ｐ、ｑは０
から２までの整数を示す。）4. A soluble polyimide composition comprising a repeating unit represented by the following general formula (4). Embedded image (Wherein R 1 and R 2 are methylene, oxygen, C (CH 3 ) 2 , C (C
F 3 ) 2 represents one of COO groups. R4 is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
Up to an alkoxy group, an ester group, a carboxyl group, and a hydroxyl group. R5 represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an R6-CO group, or an R6-OCO group. R6
Represents a hydrocarbon group having 1 to 4 carbon atoms. p and q are 0
And an integer from 2 to 2. )
される繰り返し単位を有する組成物、または一般式
（３）及び一般式（６）および一般式（７）で表される
繰り返し単位を有する組成物、または一般式（６）およ
び一般式（７）で表される繰り返し単位を有する組成物
の少なくとも１つ含有することを特徴とするポリベンゾ
オキサゾール−ポリイミド組成物 【化５】 （式中、Ｒ１、Ｒ２はメチレン、酸素、C(CH3)2、C(C
F3)2、COOのうちのいずれかの基を示す。Ｒ４は水素原
子、炭素数１から４までの炭化水素基、炭素数１から４
までのアルコキシ基、エステル基、カルボキシル基、水
酸基を示す。Ｒ５は水素原子、炭素数１から６までの炭
化水素基、Ｒ６−ＣＯ基、Ｒ６−ＯＣＯ基を示す。Ｒ６
は水素原子、炭素数１から４までの炭化水素基を示す。
ただし、Ｒ４が水酸基、炭素数１から４までのアルコキ
シ基、エステル基以外の基を表す場合、一般式（３）及
び一般式（５）であり、Ｒ４が水酸基、炭素数１から４
までのアルコキシ基、エステル基の場合は、一般式
（３）及び一般式（６）及び一般式（７）あるいは一般
式（６）及び一般式（７）となる。ｐ、ｑは０から２ま
での整数を示す。ｒ、ｓは０または１を示す。）5. A composition having a repeating unit represented by the following general formulas (3) and (5), or a composition represented by the following general formulas (3), (6) and (7): A polybenzoxazole-polyimide composition comprising at least one of a composition having a repeating unit represented by Formula (6) and a composition having a repeating unit represented by Formula (7): 5] (Wherein R 1 and R 2 are methylene, oxygen, C (CH 3 ) 2 , C (C
F 3 ) 2 represents one of COO groups. R4 is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
Up to an alkoxy group, an ester group, a carboxyl group, and a hydroxyl group. R5 represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an R6-CO group, or an R6-OCO group. R6
Represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
However, when R4 represents a group other than a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms and an ester group, the general formulas (3) and (5) are used, and R4 represents a hydroxyl group, a carbon number of 1 to 4 carbon atoms.
In the case of the above alkoxy groups and ester groups, general formulas (3) and (6) and general formula (7) or general formulas (6) and (7) are obtained. p and q each represent an integer from 0 to 2. r and s represent 0 or 1. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000343220A JP2001348428A (en) | 1999-12-22 | 2000-11-10 | Polyamic acid composition, soluble polyimide composition, and polybenzoxazole-polyimide composition |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36402299 | 1999-12-22 | ||
| JP2000-106359 | 2000-04-07 | ||
| JP11-364022 | 2000-04-07 | ||
| JP2000106359 | 2000-04-07 | ||
| JP2000343220A JP2001348428A (en) | 1999-12-22 | 2000-11-10 | Polyamic acid composition, soluble polyimide composition, and polybenzoxazole-polyimide composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001348428A true JP2001348428A (en) | 2001-12-18 |
Family
ID=27341698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000343220A Pending JP2001348428A (en) | 1999-12-22 | 2000-11-10 | Polyamic acid composition, soluble polyimide composition, and polybenzoxazole-polyimide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001348428A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035689A1 (en) * | 2002-10-16 | 2004-04-29 | Pi R & D Co., Ltd. | Solution compositions of block copolyimides comprising pyromellitic dianhydride and process for production thereof |
| US8013103B2 (en) | 2008-10-10 | 2011-09-06 | Industry-University Cooperation Foundation, Hanyang University | Polymer compounds and a preparation method thereof |
| US8163071B2 (en) | 2008-05-19 | 2012-04-24 | Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) | Hollow fiber, dope composition for forming hollow fiber, and method of preparing hollow fiber using the same |
| US8487064B2 (en) | 2008-10-10 | 2013-07-16 | Industry-University Cooperation Foundation, Hanyang University | Polymer compounds and a preparation method thereof |
| US8821617B2 (en) | 2008-02-28 | 2014-09-02 | Industry-University Cooperation Foundation, Hanyang University | Polyimide-co-polybenzoxazole copolymer, preparation method thereof, and gas separation membrane comprising the same |
| US8975110B2 (en) | 2010-04-26 | 2015-03-10 | Samsung Electronics Co., Ltd. | Methods of forming a passivation layer |
| KR20150027280A (en) * | 2012-08-03 | 2015-03-11 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Polymers, polymer membranes and methods of producing the same |
| KR20190112183A (en) | 2013-01-16 | 2019-10-02 | 닛산 가가쿠 가부시키가이샤 | Method for producing resin thin film for display substrates and composition for forming resin thin film for display substrates |
-
2000
- 2000-11-10 JP JP2000343220A patent/JP2001348428A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035689A1 (en) * | 2002-10-16 | 2004-04-29 | Pi R & D Co., Ltd. | Solution compositions of block copolyimides comprising pyromellitic dianhydride and process for production thereof |
| US8821617B2 (en) | 2008-02-28 | 2014-09-02 | Industry-University Cooperation Foundation, Hanyang University | Polyimide-co-polybenzoxazole copolymer, preparation method thereof, and gas separation membrane comprising the same |
| US8163071B2 (en) | 2008-05-19 | 2012-04-24 | Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) | Hollow fiber, dope composition for forming hollow fiber, and method of preparing hollow fiber using the same |
| US8013103B2 (en) | 2008-10-10 | 2011-09-06 | Industry-University Cooperation Foundation, Hanyang University | Polymer compounds and a preparation method thereof |
| US8232367B2 (en) | 2008-10-10 | 2012-07-31 | Industry-University Cooperation Foundation, Hanyang University | Polymer compounds and a preparation method thereof |
| US8487064B2 (en) | 2008-10-10 | 2013-07-16 | Industry-University Cooperation Foundation, Hanyang University | Polymer compounds and a preparation method thereof |
| US8975110B2 (en) | 2010-04-26 | 2015-03-10 | Samsung Electronics Co., Ltd. | Methods of forming a passivation layer |
| KR20150027280A (en) * | 2012-08-03 | 2015-03-11 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Polymers, polymer membranes and methods of producing the same |
| CN104684967A (en) * | 2012-08-03 | 2015-06-03 | 气体产品与化学公司 | Polymers, polymer membranes and methods of producing the same |
| JP2015528849A (en) * | 2012-08-03 | 2015-10-01 | エア プロダクツ アンド ケミカルズ インコーポレイテッドＡｉｒ Ｐｒｏｄｕｃｔｓ Ａｎｄ Ｃｈｅｍｉｃａｌｓ Ｉｎｃｏｒｐｏｒａｔｅｄ | Polymer, polymer film and production method thereof |
| KR101676586B1 (en) | 2012-08-03 | 2016-11-15 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Polymers, polymer membranes and methods of producing the same |
| CN104684967B (en) * | 2012-08-03 | 2017-05-17 | 气体产品与化学公司 | Polymers, polymer membranes and methods of producing the same |
| KR20190112183A (en) | 2013-01-16 | 2019-10-02 | 닛산 가가쿠 가부시키가이샤 | Method for producing resin thin film for display substrates and composition for forming resin thin film for display substrates |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5740977B2 (en) | Photosensitive polyimide precursor and photosensitive resin composition | |
| KR101751904B1 (en) | Poly silsesquinoxane resin composition for flexible substrate | |
| JP2001114893A (en) | Polybenzoxazole resin and its precursor | |
| JPH051148A (en) | All-fluorinated polyimide, intermediates and starting materials thereof, methods for producing them, and all-fluorinated polyimide optical materials | |
| JP2000128987A (en) | Polybenzoxazole precursor and polybenzoxazole | |
| WO2024082896A1 (en) | Alkali-soluble resin, photosensitive resin composition, and photosensitive cured film | |
| JP2011111596A (en) | Manufacturing method of polyimide film, and polyimide film | |
| JP2001348428A (en) | Polyamic acid composition, soluble polyimide composition, and polybenzoxazole-polyimide composition | |
| EP0811648B1 (en) | Polyimide precursor solution, process for the production thereof and process for producing a film or coating therefrom | |
| WO2010131442A1 (en) | Process for producing polyamic acid solution, and polyimide film | |
| US5714572A (en) | Polyimide resin composition | |
| JP2003105085A (en) | Material for organic insulating film and organic insulating film | |
| JP2007505973A (en) | High refractive index, polyimide used as thin film material | |
| JP2010235917A (en) | High refractive index resin composition and optical part | |
| JP4945858B2 (en) | Organic insulating film material and organic insulating film | |
| JPH02202950A (en) | Silicon polyimide precursor composition | |
| JP2022172466A (en) | Novel diamine compound, polyimide precursor and polyimide film using the same, and uses thereof | |
| JP2001323061A (en) | Low-dielectric constant polyimide composition | |
| JP3002710B2 (en) | Low particle-containing polyimide precursor, polyimide solution and method for producing the same | |
| JP2000302967A (en) | Polymer composition with low dielectric constant | |
| JP2827059B2 (en) | Fluorinated polyamic acid, fluorinated polyimide and methods for producing them | |
| JP2001199958A (en) | Diamine compound and crosslinkable polyamic acid and polyimide each using the same | |
| JP2000186146A (en) | Polybenzoxazole precursor and polybenzoxazole resin | |
| JPS6315744A (en) | Substrate for electronic part | |
| JP2000080163A (en) | Fluorinated polyimide and its precursor |