JP2005232024A - Diamine having silsesquioxane skeleton and polymer using the same - Google Patents
Diamine having silsesquioxane skeleton and polymer using the same Download PDFInfo
- Publication number
- JP2005232024A JP2005232024A JP2004039577A JP2004039577A JP2005232024A JP 2005232024 A JP2005232024 A JP 2005232024A JP 2004039577 A JP2004039577 A JP 2004039577A JP 2004039577 A JP2004039577 A JP 2004039577A JP 2005232024 A JP2005232024 A JP 2005232024A
- Authority
- JP
- Japan
- Prior art keywords
- diamine
- acid
- thin film
- perfluoro
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 150000004985 diamines Chemical class 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 title claims description 22
- 239000004642 Polyimide Substances 0.000 claims abstract description 12
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 12
- 229920001721 polyimide Polymers 0.000 claims abstract description 12
- 239000004952 Polyamide Substances 0.000 claims abstract description 10
- 229920002647 polyamide Polymers 0.000 claims abstract description 10
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 7
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 7
- -1 3,3,3-trifluoropropyl Chemical group 0.000 claims description 136
- 239000010408 film Substances 0.000 claims description 29
- 230000003287 optical effect Effects 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 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 claims description 17
- 239000010409 thin film Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 239000004973 liquid crystal related substance Substances 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004407 fluoroaryl group Chemical group 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 239000002861 polymer material Substances 0.000 abstract description 5
- 125000005017 substituted alkenyl group Chemical group 0.000 abstract 1
- 125000000547 substituted alkyl group Chemical group 0.000 abstract 1
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- LTVOKYUPTHZZQH-UHFFFAOYSA-N difluoromethane Chemical group F[C]F LTVOKYUPTHZZQH-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical class Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- YJLVXRPNNDKMMO-UHFFFAOYSA-N 3,4,5,6-tetrafluorophthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1C(O)=O YJLVXRPNNDKMMO-UHFFFAOYSA-N 0.000 description 2
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 2
- LFEWXDOYPCWFHR-UHFFFAOYSA-N 4-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C=C1 LFEWXDOYPCWFHR-UHFFFAOYSA-N 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PCJJZUQUVMVZGQ-UHFFFAOYSA-N 4-[(4,4-dicarboxycyclohexyl)methyl]cyclohexane-1,1-dicarboxylic acid Chemical compound C1CC(C(=O)O)(C(O)=O)CCC1CC1CCC(C(O)=O)(C(O)=O)CC1 PCJJZUQUVMVZGQ-UHFFFAOYSA-N 0.000 description 2
- PHQYMDAUTAXXFZ-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C=C1 PHQYMDAUTAXXFZ-UHFFFAOYSA-N 0.000 description 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- FKUJGZJNDUGCFU-UHFFFAOYSA-N 2,5-dimethylterephthalic acid Chemical compound CC1=CC(C(O)=O)=C(C)C=C1C(O)=O FKUJGZJNDUGCFU-UHFFFAOYSA-N 0.000 description 1
- RWHRIIMYBNGFEV-UHFFFAOYSA-N 2-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=CC=C1C(O)=O RWHRIIMYBNGFEV-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- SLWIPPZWFZGHEU-UHFFFAOYSA-N 2-[4-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CC(O)=O)C=C1 SLWIPPZWFZGHEU-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DPFKBFAYVWIVRK-UHFFFAOYSA-N 2-trichlorosilylethyl acetate Chemical compound CC(=O)OCC[Si](Cl)(Cl)Cl DPFKBFAYVWIVRK-UHFFFAOYSA-N 0.000 description 1
- NNOHXABAQAGKRZ-UHFFFAOYSA-N 3,5-dinitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC(C(Cl)=O)=CC([N+]([O-])=O)=C1 NNOHXABAQAGKRZ-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- KHZYMPDILLAIQY-UHFFFAOYSA-N 3-(3-carboxyphenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=C(C=CC=2)C(O)=O)=C1 KHZYMPDILLAIQY-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- IFRZFIUBFCZXKK-UHFFFAOYSA-N 3-triethoxysilylpropan-1-amine;n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCN.CO[Si](OC)(OC)CCCNCCN IFRZFIUBFCZXKK-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
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
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- UMRMNHAITOCJKK-UHFFFAOYSA-N 4-(4,4-dicarboxycyclohexyl)oxycyclohexane-1,1-dicarboxylic acid Chemical compound C(=O)(O)C1(CCC(CC1)OC1CCC(CC1)(C(=O)O)C(=O)O)C(=O)O UMRMNHAITOCJKK-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、シルセスキオキサン骨格を有するジアミン、それを用いた重合体、およびその用途に関するものである。本発明の重合体は、大規模集積回路(LSI)の絶縁膜、保護膜等の半導体材料、液晶配向膜等の表示素子用材料、および光導波路材料といった光エレクトロニクス分野に用いられる。 The present invention relates to a diamine having a silsesquioxane skeleton, a polymer using the diamine, and uses thereof. The polymer of the present invention is used in the field of optoelectronics such as semiconductor materials for large scale integrated circuits (LSI), semiconductor materials such as protective films, materials for display elements such as liquid crystal alignment films, and optical waveguide materials.
近年、エレクトロニクスの加速度的進歩に伴い、LSIの微細化、高速化が一層求められている。しかし、単純に配線を微細化するだけでは、配線遅延の増大による電送速度低下を招き、結果的に高速化が不可能になる。そこで、処理速度を低下させることなく配線を微細化するには、層間絶縁膜の誘電率を低くすることが必須条件であり、より低誘電率を目指した新材料、新手法の提案が相次いでいる。 In recent years, along with the acceleration of electronics, there is a further demand for miniaturization and higher speed of LSI. However, simply miniaturizing the wiring leads to a decrease in the transmission speed due to an increase in wiring delay, and as a result, speeding up becomes impossible. Therefore, in order to miniaturize wiring without reducing the processing speed, it is indispensable to lower the dielectric constant of the interlayer insulating film, and proposals for new materials and new methods aiming at lower dielectric constant are successively made. Yes.
現在開発されている低誘電率層間絶縁膜材料は、二酸化ケイ素をフッ素や有機成分で変性したシリカ系材料と、有機高分子材料、そして両者を複合化した有機/無機ハイブリッド材料に大別できる。特に複合材料においては、カゴ状構造を有する有機ケイ素化合物を導入し、その空孔を利用して誘電率の低減を図るナノコンポシット材料が注目されている(特許文献1参照)。この手法において用いられるカゴ状ケイ素化合物は、一般にシルセスキオキサンと総称される化合物であり、特にケイ素原子8個を含む立方体構造(以下T8と略記する)を末端、もしくは側鎖に有するポリイミドが開示されている(非特許文献1〜3参照)。しかし、非特許文献1記載のポリイミドはT8骨格を末端に有するため、T8骨格の導入量は限定される。同2記載の重合体はT8骨格を高分子反応によって後から導入するものであり、該骨格をあらかじめ有するモノマーは開示されていない。非特許文献3ではケイ素原子に結合している置換基がシクロペンチル基であるT8骨格を有するモノマーが開示されている。しかし、同官能基を含むシクロアルキル基は一般に溶媒に対する溶解性が低い。そのため、たとえ溶媒に溶解しても塗布性に劣るという欠点を有する。
Currently developed low dielectric constant interlayer insulating film materials can be broadly classified into silica-based materials in which silicon dioxide is modified with fluorine and organic components, organic polymer materials, and organic / inorganic hybrid materials in which both are combined. In particular, in composite materials, nano-composite materials that introduce an organosilicon compound having a cage structure and reduce the dielectric constant using the pores have attracted attention (see Patent Document 1). The cage-like silicon compound used in this method is a compound generally referred to as silsesquioxane, and in particular, a polyimide having a cubic structure containing 8 silicon atoms (hereinafter abbreviated as T8) at the terminal or side chain is used. It is disclosed (see Non-Patent
また、半導体以外の光エレクトロニクス分野でも、光ネットワークの拡大に伴い石英光導波路より低コストなポリマー光導波路の開発が活発化している。しかし、ポリマー光導波路は通信波長領域の伝送損失が石英に比べて大きく、それは材料中の炭素−水素結合に起因することが明らかになっている。そこで、ポリイミドやポリアクリレート等の有機ポリマー中の水素原子を重水素やフッ素原子で置換し、伝送損失を低減する手法が広く用いられている(非特許文献4参照)。しかし、シルセスキオキサンのような有機ケイ素化合物を用いて、より石英に近い分子構造を有する光導波路材料は開示されていない。 Also, in the field of optoelectronics other than semiconductors, development of polymer optical waveguides having a lower cost than quartz optical waveguides has been activated with the expansion of optical networks. However, it has been clarified that the polymer optical waveguide has a larger transmission loss in the communication wavelength region than quartz, which is caused by the carbon-hydrogen bond in the material. Therefore, a technique is widely used in which hydrogen atoms in organic polymers such as polyimide and polyacrylate are replaced with deuterium or fluorine atoms to reduce transmission loss (see Non-Patent Document 4). However, an optical waveguide material having a molecular structure closer to quartz using an organosilicon compound such as silsesquioxane is not disclosed.
本発明の目的は、低誘電率、かつ、光の伝送損失を低減することができる高分子材料を提供することであり、そのために、それを与えるT8骨格を有するジアミンを提供することである。 An object of the present invention is to provide a polymer material that has a low dielectric constant and can reduce light transmission loss, and therefore, to provide a diamine having a T8 skeleton that provides the polymer material.
本発明者らは、ポリマー側鎖にT8骨格を導入し、(1)その分子内空孔を利用して誘電率の低減を図る、(2)石英類似の分子構造とすることで光の伝送損失を低減させるという2つの観点から鋭意研究した。その結果、T8骨格を分子中に含むジアミンを合成し、それを重合させる事により、層間絶縁膜や光導波路にそれぞれ不可欠な低誘電率と低伝送損失を示すポリイミド、およびポリアミドを得る事に成功した。さらに、ポリマー中にフッ素原子を導入した場合、特にT8骨格中にフルオロアルキルを有する系において、前述の効果が顕著になることを見出し本発明の完成に至った。 The present inventors introduce a T8 skeleton into the polymer side chain, (1) reduce the dielectric constant by utilizing the intramolecular vacancies, and (2) transmit light by using a molecular structure similar to quartz. We have studied earnestly from the two viewpoints of reducing loss. As a result, we succeeded in obtaining polyimides and polyamides with low dielectric constant and low transmission loss, which are indispensable for interlayer insulation films and optical waveguides, respectively, by synthesizing and polymerizing diamine containing T8 skeleton in the molecule. did. Furthermore, when a fluorine atom is introduced into the polymer, the above-described effects are found to be remarkable particularly in a system having fluoroalkyl in the T8 skeleton, and the present invention has been completed.
すなわち、本発明のジアミンはT8骨格を分子中に含有し、テトラカルボン酸二無水物、またはジカルボン酸と公知の方法で容易に重合させることができ、所望とする重合体を得ることができる。
本発明は、以下に示す項(1)〜(20)から構成される。
That is, the diamine of the present invention contains a T8 skeleton in the molecule and can be easily polymerized with a tetracarboxylic dianhydride or dicarboxylic acid by a known method to obtain a desired polymer.
The present invention includes the following items (1) to (20).
(1) 分子中に式(1)で示されるシルセスキオキサン骨格を1または2個有するジアミン。
式(1)において、Xは独立して炭素数1〜20のアルキル、炭素数2〜20のアルケニルまたは炭素数6〜20のアリールであり、任意の−CH2−は酸素で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよい。
(1) A diamine having one or two silsesquioxane skeletons represented by formula (1) in the molecule.
In the formula (1), X is independently alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons or aryl having 6 to 20 carbons, and any —CH 2 — may be replaced with oxygen. Well, any hydrogen may be replaced with a halogen.
(2) 式(2)で示される項1に記載のジアミン。
式(2)において、Yは単結合または炭素数1〜15の2価の有機基、Zは炭素数1〜15の3価の有機基である。
(2) The diamine according to
In Formula (2), Y is a single bond or a divalent organic group having 1 to 15 carbon atoms, and Z is a trivalent organic group having 1 to 15 carbon atoms.
(3) Xがフルオロアルキルまたはフルオロアリールである項1に記載のジアミン。
(3) The diamine according to
(4) Xがフルオロアルキルまたはフルオロアリールである項2に記載のジアミン。 (4) The diamine according to Item 2, wherein X is fluoroalkyl or fluoroaryl.
(5) Xがトリフルオロメチル、3,3,3−トリフルオロプロピル、3,3,4,4,5,5,6,6,6−ノナフルオロヘキシル、トリデカフルオロ−1,1,2,2−テトラヒドロオクチル、ヘプタデカフルオロ−1,1,2,2−テトラヒドロデシル、パーフルオロ−1H,1H,2H,2H−ドデシル、パーフルオロ−1H,1H,2H,2H−テトラデシル、ペンタフルオロフェニル及び4−フルオロフェニルの何れかである項1または3に記載のジアミン。
(5) X is trifluoromethyl, 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2 , 2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perfluoro-1H, 1H, 2H, 2H-tetradecyl, pentafluorophenyl Item 4. The diamine according to
(6) Xがトリフルオロメチル、3,3,3−トリフルオロプロピル、3,3,4,4,5,5,6,6,6−ノナフルオロヘキシル、トリデカフルオロ−1,1,2,2−テトラヒドロオクチル、ヘプタデカフルオロ−1,1,2,2−テトラヒドロデシル、パーフルオロ−1H,1H,2H,2H−ドデシル、パーフルオロ−1H,1H,2H,2H−テトラデシル、ペンタフルオロフェニル及び4−フルオロフェニルの何れかである項2または4に記載のジアミン。 (6) X is trifluoromethyl, 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2 , 2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perfluoro-1H, 1H, 2H, 2H-tetradecyl, pentafluorophenyl Item 5. The diamine according to Item 2 or 4, which is any one of 4-fluorophenyl and 4-fluorophenyl.
(7) Zがベンゼントリイルまたはトリフルオロベンゼントリイルである項2、4または6に記載のジアミン。 (7) The diamine according to Item 2, 4 or 6, wherein Z is benzenetriyl or trifluorobenzenetriyl.
(8) 項1〜7の何れか1項に記載のジアミンと、テトラカルボン酸二無水物の重付加反応で得られ、重量平均分子量が5,000〜500,000であるポリアミック酸。
(8) A polyamic acid obtained by a polyaddition reaction of the diamine according to any one of
(9) 項8に記載のポリアミック酸を脱水環化して得られるポリイミド。 (9) A polyimide obtained by dehydrating and cyclizing the polyamic acid according to item 8.
(10) 項1〜7の何れか1項に記載のジアミンと、ジカルボン酸またはその誘導体の重縮合反応で得られ、重量平均分子量が5,000〜500,000であるポリアミド。
(10) A polyamide having a weight average molecular weight of 5,000 to 500,000, which is obtained by a polycondensation reaction of the diamine according to any one of
(11) 項1〜7の何れか1項に記載のジアミンと、トリカルボン酸またはその誘導体の重縮合反応で得られ、重量平均分子量が5,000〜500,000であるポリアミドイミド。
(11) Polyamideimide obtained by polycondensation reaction of the diamine according to any one of
(12) 項8〜11の何れか1項に記載の重合体からなる薄膜。 (12) A thin film comprising the polymer according to any one of items 8 to 11.
(13) 項12に記載の薄膜を用いることを特徴とする絶縁膜。 (13) An insulating film using the thin film according to item 12.
(14) 項12に記載の薄膜を用いることを特徴とする保護膜。 (14) A protective film comprising the thin film according to item 12.
(15) 項12に記載の薄膜を用いることを特徴とする液晶配向膜。 (15) A liquid crystal alignment film using the thin film according to item 12.
(16) 項12に記載の薄膜を用いることを特徴とする光導波路材料。 (16) An optical waveguide material using the thin film according to item 12.
(17) 項12に記載の絶縁膜を用いることを特徴とする電気的固体装置。 (17) An electrical solid-state device using the insulating film according to item 12.
(18) 項12に記載の保護膜を用いることを特徴とする電気的固体装置。 (18) An electrical solid device using the protective film according to item 12.
(19) 項12に記載の液晶配向膜を用いることを特徴とする液晶表示素子。 (19) A liquid crystal display element using the liquid crystal alignment film according to item 12.
(20) 項16に記載の光導波路材料を用いることを特徴とする光導波路。 (20) An optical waveguide using the optical waveguide material according to item 16.
本発明のジアミンは機械強度や耐熱性に優れた、剛直なカゴ状骨格を分子内に有している。しかも、骨格内部に空隙を持つことから、本発明のジアミンを用いた本発明の重合体は、耐熱性等に優れるだけでなく低誘電率、かつ、低光伝送損失である。さらに、T8骨格自体にフルオロアルキルを導入した本発明の重合体は、重合体の誘電率または光伝送損失をより一層低減させることができる。そのため、層間絶縁膜やポリマー光導波路等の電子材料として有用である。 The diamine of the present invention has a rigid cage structure in the molecule that is excellent in mechanical strength and heat resistance. In addition, since the voids are present inside the skeleton, the polymer of the present invention using the diamine of the present invention has not only excellent heat resistance but also low dielectric constant and low optical transmission loss. Furthermore, the polymer of the present invention in which fluoroalkyl is introduced into the T8 skeleton itself can further reduce the dielectric constant or optical transmission loss of the polymer. Therefore, it is useful as an electronic material such as an interlayer insulating film or a polymer optical waveguide.
本発明のジアミンは、通常の有機合成化学的手法で合成することが可能であるが、官能基を持つトリクロロシラン誘導体でT8前駆体を閉環し、続いてアミノ基を導入するのが最も一般的である。一般式(2)において連結基(Y)がエステル結合の場合の合成例を以下に示す。 The diamine of the present invention can be synthesized by a general organic synthetic chemistry method, but it is most common to cyclize the T8 precursor with a trichlorosilane derivative having a functional group and then introduce an amino group. It is. A synthesis example when the linking group (Y) is an ester bond in the general formula (2) is shown below.
連結基(Y)がアルキレン結合である場合の合成例を以下に示す。
Synthesis examples in the case where the linking group (Y) is an alkylene bond are shown below.
通常のトリクロロシランでT8前駆体を閉環し、しかる後に不飽和置換基を有するジアミン、またはその前駆体とヒドロシリル化する方法も有用である。その合成例を以下に示す。
It is also useful to cyclize the T8 precursor with normal trichlorosilane and then hydrosilylate with an unsaturated substituent diamine or precursor thereof. The synthesis example is shown below.
本発明のジアミンにおいて、式(1)または(2)におけるXとしては、置換または非置換アルキルの具体例として、メチル、エチル、プロピル、1−メチルエチル、ブチル、2−メチルプロピル、1,1−ジメチルエチル、ペンチル、ヘキシル、1,1,2−トリメチルプロピル、ヘプチル、オクチル、2,4,4−トリメチルペンチル、ノニル、デシル、ウンデシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル、エイコシル等のアルキル、トリフルオロメチル、ペンタフルオロエチル、3,3,3−トリフルオロプロピル、3,3,4,4,5,5,6,6,6−ノナフルオロヘキシル、トリデカフルオロ−1,1,2,2−テトラヒドロオクチル、ヘプタデカフルオロ−1,1,2,2−テトラヒドロデシル、パーフルオロ−1H,1H,2H,2H−ドデシル、パーフルオロ−1H,1H,2H,2H−テトラデシル等のフルオロアルキル、3−メトキシプロピル、メトキシエトキシウンデシル、3−ヘプタフルオロイソプロポキシプロピル等のアルコキシを挙げることができる。 In the diamine of the present invention, X in formula (1) or (2) is, as a specific example of substituted or unsubstituted alkyl, methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1 -Alkyl such as dimethylethyl, pentyl, hexyl, 1,1,2-trimethylpropyl, heptyl, octyl, 2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, etc. Fluoromethyl, pentafluoroethyl, 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2 -Tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluo -1H, 1H, 2H, 2H-dodecyl, fluoroalkyl such as perfluoro-1H, 1H, 2H, 2H-tetradecyl, alkoxy such as 3-methoxypropyl, methoxyethoxyundecyl, 3-heptafluoroisopropoxypropyl be able to.
また、置換または非置換アルケニルの具体例として、エテニル、2−プロペニル、3−ブテニル、5−ヘキセニル、7−オクテニル、10−ウンデセニル等のアルケニル、アリルオキシウンデシル等のアルケニルオキシアルキルを挙げることができる。 Specific examples of substituted or unsubstituted alkenyl include alkenyl such as ethenyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 10-undecenyl, and alkenyloxyalkyl such as allyloxyundecyl. it can.
置換または非置換のアリールとしては、フェニル、ナフチル、ペンタフルオロフェニル、4−フルオロフェニル、4−クロロフェニル、4−ブロモフェニル、4−メチルフェニル、4−エチルフェニル、4−プロピルフェニル、4−ブチルフェニル、4−ペンチルフェニル、4−ヘプチルフェニル、4−オクチルフェニル、4−ノニルフェニル、4−デシルフェニル、2,4−ジメチルフェニル、2,4,6−トリメチルフェニル、2,4,6−トリエチルフェニル、4−(1−メチルエチル)フェニル、4−(1,1−ジメチルエチル)フェニル、4−(2−エチルヘキシル)フェニル、2,4,6−トリス(1−メチルエチル)フェニル、4−メトキシフェニル、4−エトキシフェニル、4−プロポキシフェニル、4−ブトキシフェニル、4−ペンチルオキシフェニル、4−ヘプチルオキシフェニル、4−デシルオキシフェニル、4−オクタデシルオキシフェニル、4−(1−メチルエトキシ)フェニル、4−(2−メチルプロポキシ)フェニル、4−(1,1−ジメチルエトキシ)フェニル、4−エテニルフェニル、4−(1−メチルエテニル)フェニル、4−(3−ブテニル)フェニル等を挙げることができる。 Substituted or unsubstituted aryl includes phenyl, naphthyl, pentafluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl 4-pentylphenyl, 4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl, 4-decylphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl 4- (1-methylethyl) phenyl, 4- (1,1-dimethylethyl) phenyl, 4- (2-ethylhexyl) phenyl, 2,4,6-tris (1-methylethyl) phenyl, 4-methoxy Phenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4-butoxyphenyl 4-pentyloxyphenyl, 4-heptyloxyphenyl, 4-decyloxyphenyl, 4-octadecyloxyphenyl, 4- (1-methylethoxy) phenyl, 4- (2-methylpropoxy) phenyl, 4- (1,1 -Dimethylethoxy) phenyl, 4-ethenylphenyl, 4- (1-methylethenyl) phenyl, 4- (3-butenyl) phenyl and the like.
これらの中で、好ましいのは、フッ素置換されたアルキルまたはアリールであり、更に好ましいのは、トリフルオロメチル、3,3,3−トリフルオロプロピル、3,3,4,4,5,5,6,6,6−ノナフルオロヘキシル、トリデカフルオロ−1,1,2,2−テトラヒドロオクチル、ヘプタデカフルオロ−1,1,2,2−テトラヒドロデシル、パーフルオロ−1H,1H,2H,2H−ドデシル、パーフルオロ−1H,1H,2H,2H−テトラデシル、およびペンタフルオロフェニル、4−フルオロフェニルである。 Of these, preferred are fluorine-substituted alkyl or aryl, and more preferred are trifluoromethyl, 3,3,3-trifluoropropyl, 3,3,4,4,5,5, 6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H -Dodecyl, perfluoro-1H, 1H, 2H, 2H-tetradecyl, and pentafluorophenyl, 4-fluorophenyl.
式(1)または(2)において、Yは、単結合または炭素数1〜15の2価有機基であれば特に限定されない。その具体例として、メチレン、エタンジイル、プロパンジイル、ブタンジイル、ペンタンジイル、ヘキサンジイル、ヘプタンジイル、シクロブタンジイル、シクロペンタンジイル、シクロヘキサンジイル、ベンゼンジイル(フェニレン)を挙げることができる。 In Formula (1) or (2), Y is not particularly limited as long as Y is a single bond or a divalent organic group having 1 to 15 carbon atoms. Specific examples thereof include methylene, ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl and benzenediyl (phenylene).
更に、水素原子がフッ素で置換されたジフルオロメチレン、テトラフルオロエタンジイル、ヘキサフルオロプロパンジイル、オクタフルオロブタンジイル、パーフルオロペンタンジイル、パーフルオロヘキサンジイル、パーフルオロヘプタンジイル、ヘキサフルオロシクロブタンジイル、パーフルオロシクロペンタンジイル、パーフルオロシクロヘキサンジイル、フルオロベンゼンジイル(フルオロフェニレン)等の2価の基を挙げることができる。 Furthermore, difluoromethylene, tetrafluoroethanediyl, hexafluoropropanediyl, octafluorobutanediyl, perfluoropentanediyl, perfluorohexanediyl, perfluoroheptanediyl, hexafluorocyclobutanediyl, perfluoro, in which hydrogen atoms are substituted with fluorine Examples thereof include divalent groups such as cyclopentanediyl, perfluorocyclohexanediyl, and fluorobenzenediyl (fluorophenylene).
これらの炭化水素基において結合基の位置は任意である。例えば、エタンジイルの場合、1,2−エタンジイルと1,1−エタンジイルの両方の場合を含む。ベンゼンジイルは、1,4−ベンゼンジイル、1,3−ベンゼンジイル、および1,2−ベンゼンジイルの場合を含む。また、これら炭化水素の任意の−CH2−を、酸素、エステル結合、アミド結合あるいはカルボニル基で置換してもよい。このような場合、2個以上の酸素が連続する場合は化学的に不安定であるため好ましくない。 In these hydrocarbon groups, the position of the bonding group is arbitrary. For example, ethanediyl includes both 1,2-ethanediyl and 1,1-ethanediyl. Benzenediyl includes cases of 1,4-benzenediyl, 1,3-benzenediyl, and 1,2-benzenediyl. Further, any —CH 2 — of these hydrocarbons may be substituted with oxygen, an ester bond, an amide bond or a carbonyl group. In such a case, when two or more oxygen atoms are continuous, it is not preferable because it is chemically unstable.
これらの中で、好ましいYの具体例として、メチレン、エタンジイル、プロパンジイル、ブタンジイル、ペンタンジイル、ヘキサンジイル、ヘプタンジイル、ベンゼンジイル、ジフルオロメチレン、テトラフルオロエタンジイル、ヘキサフルオロプロパンジイル、オクタフルオロブタンジイル、パーフルオロペンタンジイル、パーフルオロヘキサンジイル、パーフルオロヘプタンジイルを挙げることができ、更に好ましい具体例としてメチレン、エタンジイル、プロパンジイル、ブタンジイル、ベンゼンジイル、ジフルオロメチレン、テトラフルオロエタンジイル、ヘキサフルオロプロパンジイル、オクタフルオロブタンジイルを挙げることができる。また、これらの炭素鎖中に挿入することができる置換基の具体例として好ましくは、エステル結合またはエーテル結合である。 Among these, preferred examples of Y include methylene, ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, benzenediyl, difluoromethylene, tetrafluoroethanediyl, hexafluoropropanediyl, octafluorobutanediyl, Fluoropentanediyl, perfluorohexanediyl, perfluoroheptanediyl can be mentioned, and more preferable specific examples include methylene, ethanediyl, propanediyl, butanediyl, benzenediyl, difluoromethylene, tetrafluoroethanediyl, hexafluoropropanediyl, octa Mention may be made of fluorobutanediyl. Further, specific examples of the substituent that can be inserted into these carbon chains are preferably an ester bond or an ether bond.
式(1)または(2)において、Zは、単結合か炭素数1〜15の3価有機基であれば特に限定されない。その具体的として、ベンゼントリイル、ナフタレントリイル、フルオレントリイル、アントラセントリイル、ビフェニルトリイル、トルエントリイル、キシレントリイル、ジフェニルメタントリイル等の芳香族基、エタントリイル、プロパントリイル、ブタントリイル、ペンタントリイル、ヘキサントリイル、ヘプタントリイル等の脂肪族基、シクロブタントリイル、シクロペンタントリイル、シクロヘキサントリイル、デカリントリイル、ビシクロヘキサントリイル、アダマンタントリイル等の脂環式基、ピリジントリイル、キノリントリイル、アクリジントリイル、インドールトリイル、ベンゾフラントリイル、ベンゾチオフェントリイル等の複素環構造を挙げることができる。また、これら基本骨格中の任意の水素原子をフッ素原子、またはトリフルオロメチルで置換した構造、例えばトリフルオロベンゼントリイル、ジフルオロベンゼントリイル、フルオロベンゼントリイルも炭素数1〜15以内であればよい。さらに、これら3価有機基において結合基の位置は任意である。例えば、ベンゼントリイルの場合、1,2,3−ベンゼントリイルと1,3,5−ベンゼントリイルの両方を含む。 In the formula (1) or (2), Z is not particularly limited as long as it is a single bond or a trivalent organic group having 1 to 15 carbon atoms. Specifically, aromatic groups such as benzenetriyl, naphthalenetriyl, fluorenetriyl, anthracentriyl, biphenyltriyl, toluenetoyl, xylenetriyl, diphenylmethanetriyl, ethanetriyl, propanetriyl, butanetriyl, Aliphatic groups such as pentanetriyl, hexanetriyl, heptanetriyl, cycloaliphatic groups such as cyclobutanetriyl, cyclopentanetriyl, cyclohexanetriyl, decalintriyl, bicyclohexanetriyl, adamantanetriyl, pyridine Examples include heterocyclic structures such as triyl, quinoline triyl, acridine triyl, indole triyl, benzofuran triyl, benzothiophene triyl. In addition, a structure in which any hydrogen atom in these basic skeletons is substituted with a fluorine atom or trifluoromethyl, for example, trifluorobenzenetriyl, difluorobenzenetriyl, and fluorobenzenetriyl are within 1 to 15 carbon atoms. Good. Furthermore, the position of the bonding group in these trivalent organic groups is arbitrary. For example, benzenetriyl includes both 1,2,3-benzenetriyl and 1,3,5-benzenetriyl.
これらの中で、Zの具体例として好ましくは、ベンゼントリイル、ナフタレントリイル、アントラセントリイル、ビフェニルトリイル、トリフルオロベンゼントリイル、シクロヘキサントリイル、アダマンタントリイルであり、更に好ましくはベンゼントリイルとトリフルオロベンゼントリイルである。 Among these, specific examples of Z are preferably benzenetriyl, naphthalenetriyl, anthracentriyl, biphenyltriyl, trifluorobenzenetriyl, cyclohexanetriyl, adamantanetriyl, and more preferably benzenetriyl. And trifluorobenzene triyl.
次に、1分子中にT8骨格を2個有するジアミンの製造方法について述べる。これは、
トリクロロシランでT8前駆体を閉環し、しかる後に不飽和置換基を2個有するジアミン、またはその前駆体とヒドロシリル化する方法が有用である。その合成例を以下に示す(この場合Yは3価の有機基となる)。
Next, a method for producing a diamine having two T8 skeletons in one molecule will be described. this is,
It is useful to cyclize the T8 precursor with trichlorosilane and then hydrosilylate with a diamine having two unsaturated substituents, or a precursor thereof. An example of the synthesis is shown below (in this case, Y is a trivalent organic group).
本発明のジアミンはテトラカルボン酸二無水物と重合させるとポリアミック酸が得られ、これを脱水処理すると耐熱性や機械特性に優れたポリイミドが合成できる。本発明のポリアミック酸とポリイミド製造において、モノマーとして用いるテトラカルボン酸二無水物は何の制限も受けないが、具体名を例示すると、ピロメリット酸二無水物、3,3',4,4'−ビフェニルテトラカルボン酸二無水物、2、2',3,3'−ビフェニルテトラカルボン酸二無水物、2,3,3',4'−ビフェニルテトラカルボン酸二無水物、3,3',4,4'−ベンゾフェノンテトラカルボン酸二無水物、2,3,3',4'−ベンゾフェノンテトラカルボン酸二無水物、2,2',3,3'−ベンゾフェノンテトラカルボン酸二無水物、ビス(3,4−ジカルボキシフェニル)エーテル二無水物、ビス(3,4−ジカルボキシフェニル)スルホン二無水物、1,2,5,6−ナフタレンテトラカルボン酸二無水物、2,3,6,7−ナフタレンテトラカルボン酸二無水物、ビス(ジカルボキシフェニル)メタン二無水物、シクロブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、シクロヘキサンテトラカルボン酸二無水物、ジシクロヘキサンテトラカルボン酸二無水物、ジシクロペンタンテトラカルボン酸二無水物、ビス(ジカルボキシシクロヘキシル)エーテル二無水物、ビス(ジカルボキシシクロヘキシル)スルホン二無水物、ビス(ジカルボキシシクロヘキシル)メタン二無水物、4,4'−(ヘキサフルオロイソプロピリデン)ジフタル酸二無水物を挙げることができる。これらの化合物には異性体を含むものもあるが、これらの異性体混合物であってもかまわない。また、2種以上の化合物を併用してもよい。 When the diamine of the present invention is polymerized with tetracarboxylic dianhydride, a polyamic acid is obtained, and when this is dehydrated, a polyimide excellent in heat resistance and mechanical properties can be synthesized. In the production of the polyamic acid and polyimide of the present invention, the tetracarboxylic dianhydride used as a monomer is not subject to any restriction, but specific examples are pyromellitic dianhydride, 3,3 ′, 4,4 ′. -Biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6 , 7 Naphthalenetetracarboxylic dianhydride, bis (dicarboxyphenyl) methane dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, dicyclohexanetetracarboxylic dianhydride Anhydride, dicyclopentanetetracarboxylic dianhydride, bis (dicarboxycyclohexyl) ether dianhydride, bis (dicarboxycyclohexyl) sulfone dianhydride, bis (dicarboxycyclohexyl) methane dianhydride, 4,4 ′ Mention may be made of-(hexafluoroisopropylidene) diphthalic dianhydride. Some of these compounds include isomers, but a mixture of these isomers may be used. Two or more compounds may be used in combination.
これらの中で、ピロメリット酸二無水物、3,3',4,4'−ビフェニルテトラカルボン酸二無水物、3,3',4,4'−ベンゾフェノンテトラカルボン酸二無水物、ビス(3,4−ジカルボキシフェニル)エーテル二無水物、ビス(3,4−ジカルボキシフェニル)スルホン二無水物、シクロブタンテトラカルボン酸二無水物、ビス(ジカルボキシシクロヘキシル)メタン二無水物、4,4'−(ヘキサフルオロイソプロピリデン)ジフタル酸二無水物が好ましい。 Among these, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis ( 3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, cyclobutanetetracarboxylic dianhydride, bis (dicarboxycyclohexyl) methane dianhydride, 4,4 '-(Hexafluoroisopropylidene) diphthalic dianhydride is preferred.
本発明のジアミンは、ジカルボン酸またはその誘導体と重合させるとポリアミドが得られる。本発明のポリアミドにおいて、モノマーとして用いるジカルボン酸は何の制限も受けないが、具体例として、フタル酸、イソフタル酸、テレフタル酸、2,5−ジメチルテレフタル酸、4,4'−ビフェニルジカルボン酸、3,3'−ビフェニルジカルボン酸、ナフタレンジカルボン酸、フルオレンジカルボン酸、ベンゾフェノン−2,4'−ジカルボン酸、ベンゾフェノン−4,4'−ジカルボン酸、4,4'−ジカルボキシフェニルスルホン、2,2−ビス(4−カルボキシフェニル)ヘキサフルオロプロパン等の芳香族カルボン酸、マロン酸、メチルマロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、ズベリン酸、アゼライン酸、セバシン酸、1,4−フェニレンジ酢酸等の脂肪族カルボン酸、1,4−シクロヘキサンジカルボン酸、シクロペンタメチレンジ酸、デカリンジカルボン酸等の脂環式カルボン酸を挙げることができる。また、これら化合物中の任意の炭化水素基の水素をフッ素またはトリフルオロメチルで置換した化合物、例えばテトラフルオロフタル酸等も用いることができる。これらの化合物には異性体を含むものもあるが、これらの異性体混合物であってもかまわない。また、2種以上の化合物を併用してもよい。 When the diamine of the present invention is polymerized with a dicarboxylic acid or a derivative thereof, a polyamide is obtained. In the polyamide of the present invention, the dicarboxylic acid used as a monomer is not limited, but specific examples include phthalic acid, isophthalic acid, terephthalic acid, 2,5-dimethylterephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, naphthalenedicarboxylic acid, fluorenedicarboxylic acid, benzophenone-2,4′-dicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, 4,4′-dicarboxyphenylsulfone, 2,2 -Aromatic carboxylic acids such as bis (4-carboxyphenyl) hexafluoropropane, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,4- Aliphatic carboxylic acids such as phenylenediacetic acid, 1,4-cyclohexanedicarboxylic acid , It may be mentioned cyclopentadienyl methylenedioxy acid, alicyclic carboxylic acids such as decalin dicarboxylic acid. In addition, compounds in which hydrogen of any hydrocarbon group in these compounds is substituted with fluorine or trifluoromethyl, such as tetrafluorophthalic acid, can also be used. Some of these compounds include isomers, but a mixture of these isomers may be used. Two or more compounds may be used in combination.
これらの中で、フタル酸、イソフタル酸、テレフタル酸、4,4'−ビフェニルジカルボン酸、ナフタレンジカルボン酸、フルオレンジカルボン酸、ベンゾフェノン−4,4'−ジカルボン酸、4,4'−ジカルボキシフェニルスルホン、2,2−ビス(4−カルボキシフェニル)ヘキサフルオロプロパン等、グルタル酸、アジピン酸、ピメリン酸、1,4−フェニレンジ酢酸、1,4−シクロヘキサンジカルボン酸、シクロペンタメチレンジ酸、テトラフルオロフタル酸が好ましい。 Among these, phthalic acid, isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, naphthalenedicarboxylic acid, fluorenedicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, 4,4′-dicarboxyphenylsulfone 2,2-bis (4-carboxyphenyl) hexafluoropropane, glutaric acid, adipic acid, pimelic acid, 1,4-phenylenediacetic acid, 1,4-cyclohexanedicarboxylic acid, cyclopentamethylenediacid, tetrafluoro Phthalic acid is preferred.
本発明のポリアミドにおいてモノマーに用いる上記ジカルボン酸は、そのまま重合反応に供しても何ら問題はないが、反応性の誘導体に変換してから重合させるとより穏和な条件で反応させることができる。これらの誘導体として、カルボン酸クロリド等の酸ハロゲン化物、1−ヒドロキシベンゾトリアゾリルエステル、2,4−ジニトロフェニルエステル、N−ヒドロキシスクシンイミドエステル等の活性エステルを用いることが可能である。これらの誘導体を経由する場合、最も好ましいのは酸クロリドである。 The dicarboxylic acid used as a monomer in the polyamide of the present invention has no problem even if it is subjected to a polymerization reaction as it is, but can be reacted under milder conditions when it is polymerized after being converted to a reactive derivative. As these derivatives, acid halides such as carboxylic acid chloride, and active esters such as 1-hydroxybenzotriazolyl ester, 2,4-dinitrophenyl ester, N-hydroxysuccinimide ester can be used. When these derivatives are used, acid chloride is most preferable.
本発明のジアミンは、トリカルボン酸またはその誘導体と重合させるとポリアミドイミドが得られる。具体例として、トリメリット酸、無水トリメリット酸、無水トリメリット酸クロリド、トリメリット酸トリクロリド等が挙げられ、好ましくは無水トリメリット酸クロリドである。 When the diamine of the present invention is polymerized with a tricarboxylic acid or a derivative thereof, a polyamideimide is obtained. Specific examples include trimellitic acid, trimellitic anhydride, trimellitic anhydride chloride, trimellitic acid trichloride, and the like, preferably trimellitic anhydride chloride.
本発明の重合体を合成するための反応において、用いられる溶媒は、重合反応を阻害することなく、モノマーとポリマーを溶解することができるものであれば特に制限されない。具体例として、トルエン、キシレン、メシチレン、シクロペンタノン、シクロヘキサノン、N−メチル−2−ピロリドン、ホルムアミド、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N,N−ジメチルイミダゾリジノン、ジメチルスルホキシド、ヘキサメチルリン酸トリアミド、スルホラン、γ−ブチロラクトン、テトラヒドロフラン、ジオキサン、ジクロロメタン、クロロホルム、1,2−ジクロロエタンを挙げることができる。好ましくは、シクロヘキサノン、N−メチル−2−ピロリドン、N,N−ジメチルアセトアミド、テトラヒドロフランである。これらの溶媒は、単独で用いても複数混合して使用してもよい。 In the reaction for synthesizing the polymer of the present invention, the solvent used is not particularly limited as long as it can dissolve the monomer and the polymer without inhibiting the polymerization reaction. Specific examples include toluene, xylene, mesitylene, cyclopentanone, cyclohexanone, N-methyl-2-pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl. Examples include sulfoxide, hexamethylphosphoric triamide, sulfolane, γ-butyrolactone, tetrahydrofuran, dioxane, dichloromethane, chloroform, and 1,2-dichloroethane. Cyclohexanone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide and tetrahydrofuran are preferred. These solvents may be used alone or in combination.
さらに必要により、塗布性改善などの目的で表面張力の低い溶媒を併用してもよい。具体例として、乳酸アルキル、3−メチル−3−メトキシブタノ−ル、テトラリン、イソホロン、エチレングリコ−ルモノアルキルエ−テル(エチレングリコ−ルモノブチルエ−テルなど)、ジエチレングリコ−ルモノアルキルエ−テル(ジエチレングリコ−ルモノエチルエ−テルなど)、エチレングリコ−ルモノアルキルまたはフェニルアセテ−ト、トリエチレングリコ−ルモノアルキルエ−テル、プロピレングリコ−ルモノアルキルエ−テル(プロピレングリコ−ルモノブチルエ−テルなど)、マロン酸ジアルキル(マロン酸ジエチルなど)を挙げることができる。これらの溶媒は、先の良溶媒に対して貧溶媒的なものが多い。従って、溶解成分が析出しない程度の量を添加することが好ましい。 Furthermore, if necessary, a solvent having a low surface tension may be used in combination for the purpose of improving coating properties. Specific examples include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether (such as ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (diethylene glycol monoethyl ether). -Tell etc.), ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (eg propylene glycol monobutyl ether), dialkyl malonate (malonic acid) Diethyl and the like). Many of these solvents are poor solvents with respect to the previous good solvent. Therefore, it is preferable to add such an amount that the dissolved component does not precipitate.
さらに、塗布性を改良する等の目的で用いられる界面活性剤や、帯電防止の目的等で用いられる帯電防止剤を添加することも可能である。あるいは、さらに基板との密着性を向上させるために、シランカップリング剤やチタン系のカップリング剤を配合することも可能である。 Furthermore, it is also possible to add a surfactant used for the purpose of improving coating properties and an antistatic agent used for the purpose of antistatic. Alternatively, in order to further improve the adhesion to the substrate, it is possible to add a silane coupling agent or a titanium-based coupling agent.
好ましいシランカップリング剤として、ビニルトリメトキシシラン、ビニルトリエトキシシラン、N−(2−アミノエチル)−3−アミノプロピルメチルジメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、3−アミノプロピルトリメトキシシラン、3−グリシドキシプロピルトリメトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−クロロプロピルトリメトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−メルカプトプロピルトリメトキシシランを挙げることができる。 As preferred silane coupling agents, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, Examples include 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
これらの溶媒に溶解された重合体溶液を、薄膜を形成させるために基板へ塗布する場合、通常使用されている方法を使用することができる。例えば、スピンナー法、印刷法、ディッピング法、滴下法などである。塗布の際、オリゴマー溶液の溶媒組成、濃度は重合時と同一でもよいが、反応溶媒を減圧濃縮等にてその一部または全部を一旦除去した後、最適な濃度や溶媒組成に調整してから塗布してもよい。 When a polymer solution dissolved in these solvents is applied to a substrate in order to form a thin film, a conventionally used method can be used. For example, a spinner method, a printing method, a dipping method, a dropping method, and the like. During coating, the solvent composition and concentration of the oligomer solution may be the same as those during polymerization, but once the reaction solvent is partially or wholly removed by concentration under reduced pressure, etc., it is adjusted to the optimal concentration and solvent composition. It may be applied.
また、これらの溶液を塗布した後の溶媒の乾燥方法においても、通常の層間絶縁膜、保護膜、液晶配向膜、光導波路等の形成に使用されている手法と同様な方法を用いることができる。例えば、オ−ブン、ホットプレ−ト、赤外炉などを使用できる。溶液を塗布した後は、比較的低温で溶媒を蒸発させた後、100〜500℃程度の温度で、好ましくは150〜450℃で加熱処理することが好ましい。加熱温度は一定でも段階的に昇温してもよい。加熱時間は重合体の種類によって異なるが、10〜180分程度が好ましく、さらに好ましくは約30〜90分である。なお、本加熱処理においては空気中、窒素雰囲気もしくは減圧条件下のいずれで行ってもよい。 Also, in the method of drying the solvent after applying these solutions, a method similar to the method used for forming an ordinary interlayer insulating film, protective film, liquid crystal alignment film, optical waveguide, etc. can be used. . For example, an oven, a hot plate, an infrared furnace or the like can be used. After applying the solution, it is preferable to evaporate the solvent at a relatively low temperature and then heat-treat at a temperature of about 100 to 500 ° C, preferably 150 to 450 ° C. The heating temperature may be constant or increased in steps. Although heating time changes with kinds of polymer, about 10 to 180 minutes are preferable, More preferably, it is about 30 to 90 minutes. Note that this heat treatment may be performed in air, in a nitrogen atmosphere, or under reduced pressure.
本発明の重合体であるポリアミック酸、ポリアミド、ポリアミドイミドのGPCで測定したポリスチレン換算重量平均分子量は5,000〜500,000である。塗膜性及び膜強度を考慮したためである。尚、ポリアミック酸は部分的にイミド化されたポリアミック酸をも含む。 The weight average molecular weight in terms of polystyrene measured by GPC of polyamic acid, polyamide, and polyamideimide, which are the polymers of the present invention, is 5,000 to 500,000. This is because coating properties and film strength are taken into consideration. The polyamic acid also includes partially imidized polyamic acid.
本発明の層間絶縁膜は、LSI内部の多層配線構造において、電気を通す金属配線とそれらを電気的に絶縁する機能を有する膜のことである。 The interlayer insulating film of the present invention is a film having a function of electrically insulating metal wirings that conduct electricity and those in a multilayer wiring structure inside an LSI.
本発明の保護膜は、凹凸面を持った物体をコーティングすることにより、その表面を平坦にさせる膜のことである。 The protective film of the present invention is a film that flattens the surface by coating an object having an uneven surface.
本発明の液晶配向膜は、液晶表示素子内部において液晶分子の一軸配向性と、界面におけるプレチルト角を発現させる機能を有する膜のことである。 The liquid crystal alignment film of the present invention is a film having a function of expressing uniaxial alignment properties of liquid crystal molecules and a pretilt angle at the interface inside the liquid crystal display element.
本発明の光導波路材料は、光ファイバーや光配線等の光機能素子において、光信号を特定の領域に閉じこめて入射端から出射端に導く機能を有する材料のことである。 The optical waveguide material of the present invention is a material having a function of confining an optical signal in a specific region and guiding it from an incident end to an output end in an optical functional element such as an optical fiber or an optical wiring.
本発明の電気的固体装置とは、トランジスタやダイオード等の固体素子で構成される固体回路、およびその集積体である半導体集積回路装置のことである。 The electrical solid state device of the present invention is a solid state circuit composed of solid state elements such as transistors and diodes, and a semiconductor integrated circuit device which is an integrated body thereof.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれら実施例によって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
実施例で得られた化合物の物性は以下の方法で測定した。
赤外吸収スペクトル(IR):日本分光株式会社製FT/IR−7000型を用い、室温でKBr法にて測定した。
The physical properties of the compounds obtained in the examples were measured by the following methods.
Infrared absorption spectrum (IR): Measured by KBr method at room temperature using FT / IR-7000 type manufactured by JASCO Corporation.
日本分光(株)製 GULLIVER1500シリーズ HPLCシステムを使用し、テトラヒドロフランを移動相とするGPCで測定を行った。 Using a GULLIVER 1500 series HPLC system manufactured by JASCO Corporation, measurement was performed by GPC using tetrahydrofuran as a mobile phase.
プロトンNMRスペクトル(1H−NMR):日本電子株式会社製JNM−GSX400を使用し、400MHzで溶媒にクロロホルム−dを用い、内部標準物質にテトラメチルシランを用いて室温で測定した。 Proton NMR spectrum ( 1 H-NMR): JNM-GSX400 manufactured by JEOL Ltd. was used, measured at room temperature using chloroform-d as a solvent at 400 MHz and tetramethylsilane as an internal standard substance.
シリコンNMRスペクトル(29Si−NMR):日本電子株式会社製JNM−GSX400を使用し、79MHzで溶媒にクロロホルム−dを用い、内部標準物質にテトラメチルシランを用いて室温で測定した。 Silicon NMR spectrum ( 29 Si-NMR): JNM-GSX400 manufactured by JEOL Ltd. was used, chloroform-d was used as a solvent at 79 MHz, and tetramethylsilane was used as an internal standard substance at room temperature.
熱分解温度:セイコー電子工業社製、TG/DTA−220型を用い、空気中で毎分10℃の昇温速度で測定し、5%重量減少を示した点を分解温度とした。 Thermal decomposition temperature: TG / DTA-220 manufactured by Seiko Denshi Kogyo Co., Ltd. was used and measured at a temperature increase rate of 10 ° C. per minute in the air.
誘電率:ヒューレットパッカード社製、4263B型LCRメーターを用い、直径5mm電極の1KHzにおける電気容量と、別途測定した膜厚から算出した。 Dielectric constant: Using a 4263B type LCR meter manufactured by Hewlett-Packard Company, the dielectric constant was calculated from the electric capacity at 1 KHz of an electrode having a diameter of 5 mm and the film thickness measured separately.
[1]3,5−ジアミノ安息香酸エチルエステル−ヘプタトリフルオロプロピルオクタシルセスキオキサン(式(2)において、全てのX=3,3,3,−トリフルオロプロピル、Y=−COOCH2CH2−、Z=1、3,5−ベンゼントリイル)の合成;
以下、工程毎に詳細な説明を行う。
[1] 3,5-Diaminobenzoic acid ethyl ester-heptatrifluoropropyl octasilsesquioxane (in formula (2), all X = 3,3,3, -trifluoropropyl, Y = —COOCH 2 CH 2- , Z = 1,3,5-benzenetriyl);
Hereinafter, a detailed description will be given for each process.
[1]−(1) アセトキシエチル-ヘプタトリフルオロプロピルオクタシルセスキオキサン(化合物2)の合成;
還流冷却管、温度計及び攪拌子を備えた500mlの四つ口フラスコに、化合物1(15g)、トリエチルアミン(3.9g)及びテトラヒドロフラン(100g)を導入した。次いでこの溶液にアセトキシエチルトリクロロシラン(4.65g)を速やかに加え、室温下で4時間攪拌させた。その後、フィルターろ過により固-液分離を行った後、ロータリーエバポレーターでろ液を濃縮した。この濃縮物にメタノールを加え、室温下で1時間攪拌した後、フィルターろ過により固-液分離を行った。さらに得られた固体成分にテトラヒドロフラン(50g)を加え、分液漏斗中で数回水洗した後有機層を分取し、これに無水硫酸マグネシウム(2.0g)を加え脱水乾燥を行った。これを乾固するまで濃縮し、得られた固体を減圧乾燥(75℃、5時間)に付して白色の表題化合物を得た(6.7g、収率:42.9%)。
得られた化合物のGPC測定を行った結果、単一ピークを確認し、不純物等の存在は、確認されなかった。また、1H−NMRを測定した結果、化合物2の構造であることを確認した。そのケミカルシフトを以下に示す。1H−NMR(400MHz,CDCl3)δ0.94(m,14H), 1.19(t,2H), 2.03(s,3H), 2.16(m,14H), 4.18(t,2H)。
[1]-(1) Synthesis of acetoxyethyl-heptatrifluoropropyloctasilsesquioxane (compound 2);
Compound 1 (15 g), triethylamine (3.9 g) and tetrahydrofuran (100 g) were introduced into a 500 ml four-necked flask equipped with a reflux condenser, a thermometer and a stirring bar. Next, acetoxyethyltrichlorosilane (4.65 g) was quickly added to this solution and stirred at room temperature for 4 hours. Thereafter, solid-liquid separation was performed by filter filtration, and then the filtrate was concentrated by a rotary evaporator. Methanol was added to the concentrate and stirred at room temperature for 1 hour, followed by solid-liquid separation by filter filtration. Further, tetrahydrofuran (50 g) was added to the obtained solid component, and after washing several times in a separatory funnel, the organic layer was separated, and anhydrous magnesium sulfate (2.0 g) was added thereto for dehydration drying. This was concentrated to dryness, and the resulting solid was dried under reduced pressure (75 ° C., 5 hours) to give the white title compound (6.7 g, yield: 42.9%).
As a result of GPC measurement of the obtained compound, a single peak was confirmed, and the presence of impurities and the like was not confirmed. Moreover, as a result of measuring 1 H-NMR, it was confirmed that the structure of Compound 2 was obtained. The chemical shift is shown below. 1 H-NMR (400 MHz, CDCl 3 ) δ 0.94 (m, 14H), 1.19 (t, 2H), 2.03 (s, 3H), 2.16 (m, 14H), 4.18 ( t, 2H).
[1]−(2) ヒドロキシエチル-ヘプタトリフルオロプロピルオクタシルセスキオキサン(化合物3)の合成;
還流冷却管、温度計及び攪拌子を備えた1000ml三口フラスコに化合物2(3.5g)、硫酸(1.0g)、メタノール(200g)及びAK−225((HCFC−225:CF3CF2CHCl2/CClF3/CF2CHClF混合物、旭硝子(株)製)(200g)を導入した後、窒素雰囲気下、室温にて12時間攪拌した。次いで、反応温度を45℃とし、さらに9時間攪拌した。その後、ロータリーエバポレーターを用いて濃縮した。得られた濃縮物にAK−225(200g)を加え、これを分液漏斗中でイオン交換水にて数回水洗を行った。有機層を分取した後、無水硫酸マグネシウム(2.0g)を加え脱水乾燥を行った。その後、フィルターろ過により固-液分離を行った後、ロータリーエバポレーターでろ液を濃縮した。得られた濃縮物を減圧乾燥(60℃、5時間)に付し、白色の固体を得た(2.8g、収率:84.8%)。得られた化合物のGPC測定を行った結果、単一ピークを確認し、不純物等の存在は、確認されなかった。また、1H−NMRを測定した結果、化合物3の構造であることを確認した。そのケミカルシフトを以下に示す。1H−NMR(400MHz,CDCl3)δ0.93(m,14H), 1.13(t,2H), 1.39(br,1H), 2.14(m,14H), 3.81(t,2H)。
[1]-(2) Synthesis of hydroxyethyl-heptatrifluoropropyloctasilsesquioxane (compound 3);
In a 1000 ml three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, compound 2 (3.5 g), sulfuric acid (1.0 g), methanol (200 g) and AK-225 ((HCFC-225: CF 3 CF 2 CHCl 2 / CClF 3 / CF 2 CHClF mixture (Asahi Glass Co., Ltd.) (200 g) was introduced, and the mixture was stirred for 12 hours at room temperature under a nitrogen atmosphere. After that, AK-225 (200 g) was added to the resulting concentrate, and this was washed with ion-exchanged water several times in a separatory funnel. Then, anhydrous magnesium sulfate (2.0 g) was added, followed by dehydration and drying, followed by solid-liquid separation by filter filtration and concentration of the filtrate by a rotary evaporator. The resulting concentrate was dried under reduced pressure (60 ° C., 5 hours) to obtain a white solid (2.8 g, yield: 84.8%), and GPC measurement of the obtained compound was performed. As a result, a single peak was confirmed, and the presence of impurities, etc. was not confirmed, and as a result of measuring 1 H-NMR, it was confirmed that it was the structure of Compound 3. The chemical shift is shown below. 1 H-NMR (400 MHz, CDCl 3 ) δ 0.93 (m, 14H), 1.13 (t, 2H), 1.39 (br, 1H), 2.14 (m, 14H), 3.81 (t, 2H).
[1]−(3) 3,5−ジニトロ安息香酸エチルエステル−ヘプタトリフルオロプロピルオクタシルセスキオキサン(化合物4)の合成;
化合物3(1.8g)、ジクロロメタン(50g)及びトリエチルアミン(0.24g)を攪拌子を備えた100ml三ツ口フラスコ中に導入し、ドライアイス/アセトン浴中(−20℃)、窒素雰囲気下で攪拌した。次いで3,5−ジニトロベンゾイルクロライド(0.55g)/ジクロロメタン(3.0g)溶液を調製し、速やかに反応液中に添加した。1時間ドライアイス/アセトン浴中で攪拌した後、室温下でさらに2時間攪拌した。この反応液を分液漏斗に移し、イオン交換水を用いて水層が中性になるまで、水洗を繰り返した。有機層を分取した後、無水硫酸マグネシウム(2.0g)を加え脱水乾燥を行った。その後、フィルターろ過により固-液分離を行った後、ロータリーエバポレーターを用いて、ろ液を濃縮した。得られた濃縮物にメタノール(20g)を加え室温で1時間攪拌した。次いでフィルターろ過により固-液分離を行った後、固体成分を減圧乾燥(60℃、5時間)に付し、白色の固体を得た(収量:1.32g、収率:63.2%)。得られた化合物のGPC測定を行った結果、単一ピークを確認し、不純物等の存在は、確認されなかった。
また、1H−NMRを測定した結果、化合物4の構造であることを確認した。そのケミカルシフトを以下に示す。1H−NMR(400MHz,CDCl3)δ0.96(m,14H), 1.42(t,2H), 2.15(m,14H), 4.57(q,2H),9.15,9.23(AB,3H) 。
[1]-(3) Synthesis of 3,5-dinitrobenzoic acid ethyl ester-heptatrifluoropropyloctasilsesquioxane (compound 4);
Compound 3 (1.8 g), dichloromethane (50 g) and triethylamine (0.24 g) were introduced into a 100 ml three-necked flask equipped with a stirrer and stirred in a dry ice / acetone bath (−20 ° C.) under a nitrogen atmosphere. did. Next, a 3,5-dinitrobenzoyl chloride (0.55 g) / dichloromethane (3.0 g) solution was prepared and quickly added to the reaction solution. After stirring in a dry ice / acetone bath for 1 hour, the mixture was further stirred at room temperature for 2 hours. The reaction solution was transferred to a separatory funnel and washed with water until the aqueous layer became neutral using ion-exchanged water. After separating the organic layer, anhydrous magnesium sulfate (2.0 g) was added and dehydrated and dried. Thereafter, solid-liquid separation was performed by filter filtration, and then the filtrate was concentrated using a rotary evaporator. Methanol (20 g) was added to the resulting concentrate and stirred at room temperature for 1 hour. Subsequently, solid-liquid separation was performed by filter filtration, and then the solid component was dried under reduced pressure (60 ° C., 5 hours) to obtain a white solid (yield: 1.32 g, yield: 63.2%). . As a result of GPC measurement of the obtained compound, a single peak was confirmed, and the presence of impurities and the like was not confirmed.
Moreover, as a result of measuring 1 H-NMR, it was confirmed that the structure of Compound 4 was obtained. The chemical shift is shown below. 1 H-NMR (400 MHz, CDCl 3 ) δ 0.96 (m, 14H), 1.42 (t, 2H), 2.15 (m, 14H), 4.57 (q, 2H), 9.15, 9.23 (AB, 3H).
[1]−(4) 3,5−ジアミノ安息香酸エチルエステル−ヘプタトリフルオロプロピルオクタシルセスキオキサン(化合物5)の合成;
化合物4(1.2g)、10%パラジウム−炭素(和光純薬(株)製)、溶媒として酢酸エチルを用い、攪拌子を備えた50ml丸底フラスコに導入した。反応器に水素ガスを充填したガス採取袋を装着し、フラスコ内を水素ガスで数回置換した後、水素雰囲気下室温で8時間激しく攪拌した。次いで触媒をフィルターろ過にて固液分離した後、ろ液に無水硫酸マグネシウムを加え脱水乾燥を行った。その後、フィルターろ過により固-液分離を行った後、ロータリーエバポレーターを用いて、ろ液を濃縮した。得られた濃縮物を減圧乾燥(80℃、6時間)に付し、淡黄色の固体を得た(収量:0.88g、収率:81%)。得られた化合物のGPC測定を行った結果、単一ピークを確認し、不純物等の存在は、確認されなかった。このIRスペクトルを図1に示した。
また、NMRを測定した結果、化合物5の構造であることを確認した。そのケミカルシフトを以下に示す。1H−NMR(400MHz,CDCl3)δ0.48(m,14H), 1.32(t,2H), 2.13(m,14H), 3.66(br,4H),4.40(q,2H),6.17,6.74(AB,3H) 。29Si−NMR(79MHz,CDCl3)δ−67.62,−67.72,−68.52。
[1]-(4) Synthesis of 3,5-diaminobenzoic acid ethyl ester-heptatrifluoropropyloctasilsesquioxane (compound 5);
Compound 4 (1.2 g), 10% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) and ethyl acetate as a solvent were introduced into a 50 ml round bottom flask equipped with a stir bar. A gas sampling bag filled with hydrogen gas was attached to the reactor, the inside of the flask was replaced with hydrogen gas several times, and then vigorously stirred at room temperature for 8 hours in a hydrogen atmosphere. Next, the catalyst was subjected to solid-liquid separation by filter filtration, and anhydrous magnesium sulfate was added to the filtrate for dehydration drying. Thereafter, solid-liquid separation was performed by filter filtration, and then the filtrate was concentrated using a rotary evaporator. The obtained concentrate was dried under reduced pressure (80 ° C., 6 hours) to obtain a pale yellow solid (yield: 0.88 g, yield: 81%). As a result of GPC measurement of the obtained compound, a single peak was confirmed, and the presence of impurities and the like was not confirmed. The IR spectrum is shown in FIG.
Moreover, as a result of measuring NMR, it confirmed that it was the structure of the compound 5. The chemical shift is shown below. 1 H-NMR (400 MHz, CDCl 3 ) δ 0.48 (m, 14H), 1.32 (t, 2H), 2.13 (m, 14H), 3.66 (br, 4H), 4.40 ( q, 2H), 6.17, 6.74 (AB, 3H). 29 Si-NMR (79 MHz, CDCl 3 ) δ-67.62, −67.72, −68.52.
[2]−(1) ポリアミック酸の合成
上記[1]で合成したジアミン0.1700g(0.13mmol)を1−メチル−2−ピロリドン(NMP)0.92gに溶かし室温で撹拌した。この溶液に、4,4'−(ヘキサフルオロイソプロピリデン)ジフタル酸二無水物0.0592g(0.13mmol)を固体のまま添加した。室温で3時間撹拌して得られたワニスを、シクロヘキサノン0.38gで濃度15%まで希釈し、0.5ミクロンのメンブランフィルターでろ過することによってポリアミック酸の溶液を得た。GPCで測定した重量平均分子量は30800であった。
[2]-(1) Synthesis of polyamic acid 0.1700 g (0.13 mmol) of the diamine synthesized in the above [1] was dissolved in 0.92 g of 1-methyl-2-pyrrolidone (NMP) and stirred at room temperature. To this solution, 0.0592 g (0.13 mmol) of 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride was added as a solid. The varnish obtained by stirring at room temperature for 3 hours was diluted with 0.38 g of cyclohexanone to a concentration of 15%, and filtered through a 0.5 micron membrane filter to obtain a polyamic acid solution. The weight average molecular weight measured by GPC was 30800.
[2]−(2) ポリイミドの合成;
[2]−(1)で調製した溶液をスピンナー法でガラス基板に塗布し、100℃のホットプレート上で3分間加熱した。続いて窒素雰囲気下230℃のオーブンに入れて1時間焼成したところ、膜厚約820nmのポリイミドの淡黄色薄膜が得られた。
薄膜を基板から一部削り落とし、IRスペクトルを測定した結果を図2に示す。また、薄膜を削って得た粉末の熱分解温度は359.9℃であった。
[2]-(2) Synthesis of polyimide;
The solution prepared in [2]-(1) was applied to a glass substrate by a spinner method and heated on a hot plate at 100 ° C. for 3 minutes. Subsequently, when placed in an oven at 230 ° C. in a nitrogen atmosphere and baked for 1 hour, a pale yellow thin film of polyimide having a thickness of about 820 nm was obtained.
FIG. 2 shows the result of measuring the IR spectrum after partially removing the thin film from the substrate. The thermal decomposition temperature of the powder obtained by shaving the thin film was 359.9 ° C.
[3] 誘電率測定
基板を4インチシリコンウエハ(三菱住友シリコン(株)製、比抵抗0.02Ω以下、N型)に換える以外は、[2]と同様の操作で厚さ817.3nmの薄膜を形成した。この薄膜表面にマスクを介してアルミニウムを真空蒸着し、直径5mmの電極を9点作成した。続いて、LCRメーターで各点の電気容量を測定し平均値を求めたところ、548.7pF(1KHz)であった。以上の結果から誘電率を算出すると2.58であった。
[3] Dielectric constant measurement The thickness of 817.3 nm is the same as in [2] except that the substrate is replaced with a 4-inch silicon wafer (Mitsubishi Sumitomo Silicon Co., Ltd., specific resistance 0.02Ω or less, N type) A thin film was formed. Aluminum was vacuum-deposited on the surface of this thin film through a mask, and nine electrodes having a diameter of 5 mm were prepared. Then, when the electric capacity of each point was measured with the LCR meter and the average value was calculated | required, it was 548.7 pF (1 KHz). The dielectric constant calculated from the above results was 2.58.
[4] ポリアミドの合成
上記[1]で合成したジアミン0.1700g(0.13mmol)をNMP1.11gに溶かし氷冷下で撹拌した。この溶液に、テレフタル酸ジクロリド0.0264g(0.13mmol)を固体のまま添加した。室温に戻して3時間撹拌し、反応液をメタノール100ml中に投入してポリマーを沈殿させた。沈殿物をろ集し、白色の固体を減圧下乾燥してポリアミドを0.1626g得た。GPCで測定した重量平均分子量は52100であった。この粉末の熱分解温度は331.4℃であった。
[4] Synthesis of polyamide 0.1700 g (0.13 mmol) of the diamine synthesized in [1] above was dissolved in 1.11 g of NMP and stirred under ice cooling. To this solution, 0.0264 g (0.13 mmol) of terephthalic acid dichloride was added as a solid. After returning to room temperature and stirring for 3 hours, the reaction solution was poured into 100 ml of methanol to precipitate a polymer. The precipitate was collected by filtration, and the white solid was dried under reduced pressure to obtain 0.1626 g of polyamide. The weight average molecular weight measured by GPC was 52100. The thermal decomposition temperature of this powder was 331.4 ° C.
[5] ポリアミドイミドの合成
無水トリメリット酸クロリド0.0274g(0.13mmol)、トリエチルアミン0.10mlをNMP0.5gに溶解させ、氷冷下で撹拌した。その溶液に上記[1]で合成したジアミン0.1700g(0.13mmol)をNMP1.0gに溶解した溶液を滴下し、反応を行った。析出したトリエチルアミンの塩酸塩をろ別し、ろ液をスピンナー法でガラス基板に塗布し、100℃のホットプレート上で3分間加熱した。続いて窒素雰囲気下150℃のオーブンに入れて1時間焼成したところ、膜厚約900nmのポリアミドイミドの淡黄色薄膜が得られた。また、焼成前の溶液をGPCで測定した重量平均分子量は24600であった。
[5] Synthesis of polyamideimide 0.0274 g (0.13 mmol) of trimellitic anhydride chloride and 0.10 ml of triethylamine were dissolved in 0.5 g of NMP and stirred under ice cooling. A solution prepared by dissolving 0.1700 g (0.13 mmol) of the diamine synthesized in [1] above in 1.0 g of NMP was added dropwise to the solution to carry out a reaction. The precipitated hydrochloride of triethylamine was filtered off, the filtrate was applied to a glass substrate by a spinner method, and heated on a hot plate at 100 ° C. for 3 minutes. Subsequently, when placed in an oven at 150 ° C. in a nitrogen atmosphere and baked for 1 hour, a pale yellow thin film of polyamideimide having a thickness of about 900 nm was obtained. Moreover, the weight average molecular weight which measured the solution before baking by GPC was 24600.
Claims (20)
式(1)において、Xは独立して炭素数1〜20のアルキル、炭素数2〜20のアルケニルまたは炭素数6〜20のアリールであり、任意の−CH2−は酸素で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよい。 A diamine having one or two silsesquioxane skeletons represented by formula (1) in the molecule.
In the formula (1), X is independently alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons or aryl having 6 to 20 carbons, and any —CH 2 — may be replaced with oxygen. Well, any hydrogen may be replaced with a halogen.
式(2)において、Yは単結合または炭素数1〜15の2価の有機基、Zは炭素数1〜15の3価の有機基である。 The diamine according to claim 1, which is represented by the formula (2).
In Formula (2), Y is a single bond or a divalent organic group having 1 to 15 carbon atoms, and Z is a trivalent organic group having 1 to 15 carbon atoms.
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