TWI695028B - Method for producing polyimide laminate and use thereof - Google Patents
Method for producing polyimide laminate and use thereof Download PDFInfo
- Publication number
- TWI695028B TWI695028B TW105105160A TW105105160A TWI695028B TW I695028 B TWI695028 B TW I695028B TW 105105160 A TW105105160 A TW 105105160A TW 105105160 A TW105105160 A TW 105105160A TW I695028 B TWI695028 B TW I695028B
- Authority
- TW
- Taiwan
- Prior art keywords
- polyamic acid
- acid solution
- polyimide
- solvent
- substrate
- Prior art date
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 163
- 239000004642 Polyimide Substances 0.000 title claims abstract description 158
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 175
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000002904 solvent Substances 0.000 claims abstract description 81
- 239000000758 substrate Substances 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 48
- 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 40
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 150000004985 diamines Chemical class 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 23
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 17
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 claims 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 176
- 239000010410 layer Substances 0.000 description 65
- 239000011521 glass Substances 0.000 description 46
- 239000004952 Polyamide Substances 0.000 description 27
- 229920002647 polyamide Polymers 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- -1 3,4-dicarboxyphenyl Chemical group 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 239000010408 film Substances 0.000 description 17
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000001408 amides Chemical class 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 210000005069 ears Anatomy 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 4
- 235000021286 stilbenes Nutrition 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000003221 volumetric titration Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- IXFAHCCRDSSCPX-UHFFFAOYSA-N 2,5-diethylpyridine Chemical compound CCC1=CC=C(CC)N=C1 IXFAHCCRDSSCPX-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- XWQDPPJDXCZWQE-UHFFFAOYSA-N 2-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1N XWQDPPJDXCZWQE-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- AHYFYQKMYMKPKD-UHFFFAOYSA-N 3-ethoxysilylpropan-1-amine Chemical compound CCO[SiH2]CCCN AHYFYQKMYMKPKD-UHFFFAOYSA-N 0.000 description 1
- YMTRNELCZAZKRB-UHFFFAOYSA-N 3-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=CC(N)=C1 YMTRNELCZAZKRB-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
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- HPUJEBAZZTZOFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)-2,2-dimethylpropoxy]aniline Chemical compound C=1C=C(N)C=CC=1OCC(C)(C)COC1=CC=C(N)C=C1 HPUJEBAZZTZOFL-UHFFFAOYSA-N 0.000 description 1
- QBSMHWVGUPQNJJ-UHFFFAOYSA-N 4-[4-(4-aminophenyl)phenyl]aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(C=2C=CC(N)=CC=2)C=C1 QBSMHWVGUPQNJJ-UHFFFAOYSA-N 0.000 description 1
- QZLNSNIHXKQIIS-UHFFFAOYSA-N 4-pentoxyaniline Chemical compound CCCCCOC1=CC=C(N)C=C1 QZLNSNIHXKQIIS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ABTLLKINSDJQHL-UHFFFAOYSA-N NC1=CC=C(OC2=CC=C(C=C2)C2=C(C=3C=CC4=CC=CC=C4C3C=C2)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1 Chemical compound NC1=CC=C(OC2=CC=C(C=C2)C2=C(C=3C=CC4=CC=CC=C4C3C=C2)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1 ABTLLKINSDJQHL-UHFFFAOYSA-N 0.000 description 1
- NYZFNIUYLPDHPL-UHFFFAOYSA-N NC=1C=C(OC2=CC=C(C=C2)C2=C(C=3C=CC4=CC=CC=C4C3C=C2)C2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1 Chemical compound NC=1C=C(OC2=CC=C(C=C2)C2=C(C=3C=CC4=CC=CC=C4C3C=C2)C2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1 NYZFNIUYLPDHPL-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- G—PHYSICS
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Abstract
本發明提供一種具有表面充分平滑之聚醯亞胺層之聚醯亞胺積層體之製造方法等。於該製造方法中，包括將含有聚醯胺酸與溶劑之聚醯胺酸溶液塗佈於基板上而於該基板上形成聚醯亞胺層之步驟，溶劑包含選自特定之溶劑群A中之至少一種、及N-甲基-2-吡咯啶酮，並且聚醯胺酸溶液之黏度為1.0Pa‧s以上且20.0Pa‧s以下。 The present invention provides a method for manufacturing a polyimide laminate having a polyimide layer with a sufficiently smooth surface and the like. The manufacturing method includes the steps of applying a polyamic acid solution containing polyamic acid and a solvent on a substrate and forming a polyimide layer on the substrate. The solvent includes a specific solvent group A At least one of them, and N-methyl-2-pyrrolidone, and the viscosity of the polyamic acid solution is 1.0 Pa‧s or more and 20.0 Pa‧s or less.
Description
本發明係關於一種聚醯亞胺積層體之製造方法及軟性裝置之製造方法。 The invention relates to a method for manufacturing a polyimide laminate and a method for manufacturing a flexible device.
目前，於平板顯示器及電子紙等電子裝置之領域中，作為基板，主要使用玻璃基板。但是，玻璃基板由於較重且容易損壞，故而對於電子裝置而言，並不是理想之基板。因此，業界正積極地進行欲實現將基板自玻璃替換為聚合物材料之軟性裝置之研究。然而，該等技術之大多數由於需要新的生產技術及裝置，故而使用聚合物材料之軟性裝置並未大量生產。 At present, in the field of electronic devices such as flat panel displays and electronic paper, glass substrates are mainly used as substrates. However, since the glass substrate is heavy and easily damaged, it is not an ideal substrate for electronic devices. Therefore, the industry is actively conducting research on flexible devices that want to replace the substrate from glass to polymer materials. However, most of these technologies require new production technologies and devices, so soft devices using polymer materials have not been mass-produced.
另一方面，最近，作為有效率地大量生產軟性裝置之捷徑，提出有藉由使用於玻璃基板上形成有聚醯亞胺樹脂層之積層體，利用通常之玻璃基板用製程生產軟性裝置。於使用該積層體之製程中，於最後階段將聚醯亞胺樹脂層自玻璃基板分離而獲得軟性裝置。 On the other hand, recently, as a shortcut to efficiently mass-produce flexible devices, it has been proposed to produce a flexible device using a conventional glass substrate manufacturing process by using a laminate having a polyimide resin layer formed on a glass substrate. In the process of using the laminate, the polyimide resin layer is separated from the glass substrate at the final stage to obtain a flexible device.
該製程中，對於積層體要求有益於良好之操作之平滑性及低翹曲。即，積層體之聚醯亞胺層需要具有充分之表面之平滑性、及與玻璃相同程度之線膨脹係數。再者，通常用作玻璃基板之鈉鈣玻璃之線膨脹係數為8~9ppm/K左右，無鹼玻璃之線膨脹係數為3~5ppm/K左右。 In this process, the laminate requires smoothness and low warpage which are good for good operation. That is, the polyimide layer of the laminate needs to have sufficient surface smoothness and a linear expansion coefficient similar to that of glass. Furthermore, the linear expansion coefficient of soda lime glass commonly used as a glass substrate is about 8 to 9 ppm/K, and the linear expansion coefficient of alkali-free glass is about 3 to 5 ppm/K.
又，非晶矽薄膜電晶體製造時之製程溫度最高達到300~350℃。由於通常之聚醯亞胺之線膨脹係數比玻璃大，故而適於該製程之材料自然受到限制。 In addition, the manufacturing process temperature of amorphous silicon thin film transistors can reach up to 300~350℃. Since the linear expansion coefficient of ordinary polyimide is larger than that of glass, materials suitable for this process are naturally limited.
例如，專利文獻1中記載有一種於無機基板上流延由3,3',4,4'-聯苯四羧酸二酐與對苯二胺及4,4"-二胺基對聯三苯所獲得之聚醯亞胺前驅物之溶液並進行熱醯亞胺化而獲得積層體之方法。 For example, Patent Document 1 describes a casting method consisting of 3,3',4,4'-biphenyltetracarboxylic dianhydride, p-phenylenediamine, and 4,4"-diamino-p-terphenyl on an inorganic substrate. A method of obtaining a solution of the obtained polyimide precursor and performing thermal imidization to obtain a laminate.
又，專利文獻2中記載有一種對於半導體保護膜或層間絕緣膜等電子材料之製造有用之加工性優異之感光性聚醯亞胺前驅物組合物。於該聚醯亞胺前驅物溶液中使用N-甲基-2-吡咯啶酮與4-甲基-2-戊酮之混合溶劑。 In addition, Patent Document 2 describes a photosensitive polyimide precursor composition excellent in processability useful for the production of electronic materials such as semiconductor protective films and interlayer insulating films. A mixed solvent of N-methyl-2-pyrrolidone and 4-methyl-2-pentanone was used in the polyimide precursor solution.
專利文獻3中記載有一種聚醯亞胺樹脂膜之製造方法，其特徵在於：將含有包含以特定之式表示之重複單元之聚醯亞胺樹脂、及有機溶劑之聚醯亞胺樹脂溶液塗佈於基板上之後，去除有機溶劑，且去除有機溶劑之步驟係至少以2階段之溫度使塗膜乾燥之步驟。 Patent Document 3 describes a method for manufacturing a polyimide resin film, which is characterized by coating a polyimide resin solution containing a polyimide resin containing a repeating unit represented by a specific formula and an organic solvent After being placed on the substrate, the organic solvent is removed, and the step of removing the organic solvent is a step of drying the coating film at a temperature of at least two stages.
專利文獻4中記載有一種聚醯亞胺前驅物溶液，其特徵在於：其係藉由酸成分與胺成分之反應而製造，將作為具有以特定之結構式表示之重複單元之聚醯胺酸之均聚物或共聚物之聚醯亞胺前驅物溶解於包含沸點未達100℃之低沸點溶劑之1種或2種以上及沸點為100℃以上之高沸點溶劑之1種或2種以上且以全部溶劑之5~55質量%之範圍含有上述高沸點溶劑之混合溶劑。 Patent Document 4 describes a polyimide precursor solution, which is produced by the reaction of an acid component and an amine component, and will be a polyamic acid having a repeating unit represented by a specific structural formula The polyimide precursor of the homopolymer or copolymer is dissolved in one or more types of low-boiling solvents containing a boiling point less than 100°C and one or more than two types of high-boiling solvents having a boiling point of 100°C or higher And the mixed solvent containing the above high boiling point solvent in the range of 5 to 55% by mass of all solvents.
專利文獻5中記載有一種聚醯胺酸系清漆，其係包含聚合物0.1-40重量%及溶劑60-99.9重量%者，其特徵在於：溶劑係含有作為第1成分之選自特定之化合物群(A)中之至少1種化合物之5-80重量%、及作為第2成分之選自特定之化合物群B中之至少1種化合物之95-20重量%之混合溶劑。 Patent Document 5 describes a polyamic acid-based varnish containing 0.1-40% by weight of a polymer and 60-99.9% by weight of a solvent, characterized in that the solvent contains a specific compound selected as the first component A mixed solvent of 5-80% by weight of at least one compound in the group (A) and 95-20% by weight of at least one compound selected from the specific compound group B as the second component.
[專利文獻1]日本公開專利公報「日本專利特開2012-35583號(2012年2月23日公開)」 [Patent Document 1] Japanese Published Patent Gazette "Japanese Patent Laid-Open No. 2012-35583 (published on February 23, 2012)"
[專利文獻2]日本公開專利公報「日本專利特開2001-89563號(2001年4月3日公開)」 [Patent Document 2] Japanese Published Patent Gazette "Japanese Patent Laid-Open No. 2001-89563 (published on April 3, 2001)"
[專利文獻3]日本公開專利公報「日本專利特開2012-77130號(2012年4月19日公開)」 [Patent Document 3] Japanese Published Patent Gazette "Japanese Patent Laid-Open No. 2012-77130 (published on April 19, 2012)"
[專利文獻4]國際公開第03/074587號說明書(2003年9月12日公開) [Patent Document 4] International Publication No. 03/074587 (published on September 12, 2003)
[專利文獻5]日本公開專利公報「日本專利特開平10-7985號(1998年1月13日公開)」 [Patent Document 5] Japanese Published Patent Gazette "Japanese Patent Laid-Open No. 10-7985 (published on January 13, 1998)"
於專利文獻1中，報告有顯示低熱膨脹性之特定結構之聚醯亞胺前驅物，但對聚醯亞胺層之表面平滑性未作任何討論。又，於專利文獻2中，為了獲得塗佈均勻性，以所使用之單體之比率控制溶液特性，未說明混合溶劑對塗膜之表面性之效果。 In Patent Document 1, a polyimide precursor with a specific structure showing low thermal expansion is reported, but the surface smoothness of the polyimide layer is not discussed at all. In addition, in Patent Document 2, in order to obtain coating uniformity, the solution characteristics are controlled by the ratio of monomers used, and the effect of the mixed solvent on the surface properties of the coating film is not described.
又，就表面平滑性之觀點而言，專利文獻3~5中所記載之技術亦有改善之餘地。 In addition, from the viewpoint of surface smoothness, the techniques described in Patent Documents 3 to 5 also have room for improvement.
本發明係鑒於上述背景而完成者。並且，其目的係具有表面充分平滑之聚醯亞胺層之聚醯亞胺積層體等之製造方法。 The present invention was completed in view of the above background. Moreover, the object is a method of manufacturing a polyimide laminate having a polyimide layer with a sufficiently smooth surface.
於具備聚醯亞胺層及基板之聚醯亞胺積層體之製造方法中，包括將含有由四羧酸二酐與二胺合成之聚醯胺酸、及溶劑之聚醯胺酸溶液塗佈於基板上而於該基板上形成聚醯亞胺層之步驟。 The method for manufacturing a polyimide laminate having a polyimide layer and a substrate includes coating a polyamic acid solution containing a polyamic acid synthesized from a tetracarboxylic dianhydride and a diamine, and a solvent The step of forming a polyimide layer on the substrate.
並且，聚醯胺酸溶液中所含之溶劑包含選自由4-甲基-2-戊酮、環己酮、四氫呋喃、及二甲苯所組成之溶劑群A中之至少1種、及N- 甲基-2-吡咯啶酮。進而，聚醯胺酸溶液之黏度為1.0Pa．s以上且20.0Pa．s以下。 In addition, the solvent contained in the polyamic acid solution includes at least one selected from the solvent group A consisting of 4-methyl-2-pentanone, cyclohexanone, tetrahydrofuran, and xylene, and N- Methyl-2-pyrrolidone. Furthermore, the viscosity of the polyamic acid solution is 1.0 Pa. s above and 20.0Pa. s below.
根據本發明，藉由使用溶劑為混合溶劑之聚醯胺酸溶液，於將該溶液流延於無機基板上並進行加熱而製造聚醯亞胺積層體之情形時，由該聚醯亞胺積層體獲得表面之平滑性優異之聚醯亞胺層。 According to the present invention, by using a polyamic acid solution with a solvent as a mixed solvent, when the solution is cast on an inorganic substrate and heated to produce a polyimide laminate, the polyimide laminate A polyimide layer with excellent surface smoothness is obtained.
若對本發明之一實施形態進行說明則如下所述，但本發明並不限定於此。再者，本說明書中，關於數值範圍記載為「A~B」之情形時，該記載意指「A以上且B以下」。 An embodiment of the present invention will be described as follows, but the present invention is not limited to this. In addition, in this specification, when the numerical range is described as "A to B", the description means "A or more and B or less".
<用於聚醯胺酸溶液之溶劑> <Solvent used in polyamic acid solution>
通常，於溶劑中，使作為聚醯胺酸之原料之四羧酸二酐與二胺聚合，藉此獲得於該溶劑中溶解有聚醯胺酸之聚醯胺酸溶液。 Generally, tetracarboxylic dianhydride which is a raw material of polyamic acid and diamine are polymerized in a solvent, thereby obtaining a polyamic acid solution in which polyamic acid is dissolved in the solvent.
又，通常，於聚醯胺酸之聚合中，較佳為使用例如N-甲基-2-吡咯啶酮(以下，有時亦稱為NMP)、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、或γ-丁內酯等非質子性極性溶劑。再者，作為用於聚醯胺酸之聚合之溶劑，就合成聚醯胺酸之原料及聚醯胺酸之溶解性優異、進而聚醯胺酸溶液之儲存穩定性優異而言，亦可謂NMP較佳。 In addition, in general, for the polymerization of polyamic acid, it is preferable to use, for example, N-methyl-2-pyrrolidone (hereinafter sometimes also referred to as NMP), N,N-dimethylformamide, Aprotic polar solvents such as N,N-dimethylacetamide or γ-butyrolactone. In addition, as a solvent for the polymerization of polyamic acid, the raw material for synthesizing polyamic acid and the solubility of polyamic acid are excellent, and further the storage stability of polyamic acid solution is excellent, which can also be called NMP Better.
又，於聚醯胺酸溶液中，除NMP以外，為了使聚醯亞胺層之表面平滑，較佳為混合選自由4-甲基-2-戊酮(以下，有時稱為MIBK)、環己酮、四氫呋喃(以下，有時稱為THF)、及二甲苯所組成之溶劑群中之至少1種溶劑。 In addition, in the polyamic acid solution, in addition to NMP, in order to smooth the surface of the polyimide layer, it is preferably mixed with 4-methyl-2-pentanone (hereinafter sometimes referred to as MIBK), At least one solvent in the solvent group consisting of cyclohexanone, tetrahydrofuran (hereinafter sometimes referred to as THF), and xylene.
該等溶劑可於聚合時預先與NMP混合，於混合溶劑中使聚醯胺 酸聚合，亦可以NMP單獨體進行聚醯胺酸聚合，其後添加選自上述溶劑群中之溶劑。選自上述溶劑群中之溶劑相對於聚醯胺酸溶液中所含之全部溶劑，較佳為含有3重量%以上且30重量%以下，更佳為4重量%以上且25重量%以下，進而較佳為5重量%以上且15重量%以下，尤佳為5重量%以上且10重量%以下。又，於上述聚醯胺酸溶液中所含之溶劑中，N-甲基-2-吡咯啶酮與溶劑群A所包含之溶劑之重量比較佳為85：15~95：5，進而較佳為90：10~95：5。若溶劑之重量比為上述範圍，則就聚醯亞胺層之表面之平滑化效果之觀點而言較佳。再者，上述溶劑群之中，就表面之平滑化效果之觀點而言，亦可選擇MIBK。 These solvents can be mixed with NMP in advance during the polymerization, and the polyamide can be used in the mixed solvent In the acid polymerization, the polyamide can be polymerized with NMP alone, and then a solvent selected from the above-mentioned solvent group is added. The solvent selected from the above solvent group preferably contains 3% by weight or more and 30% by weight or less, and more preferably 4% by weight or more and 25% by weight or less with respect to all the solvents contained in the polyamic acid solution. It is preferably 5% by weight or more and 15% by weight or less, and particularly preferably 5% by weight or more and 10% by weight or less. In addition, in the solvent contained in the above polyamic acid solution, the weight of N-methyl-2-pyrrolidone and the solvent contained in the solvent group A is preferably 85:15~95:5, and more preferably It is 90:10~95:5. If the weight ratio of the solvent is within the above range, it is preferable from the viewpoint of the smoothing effect of the surface of the polyimide layer. In addition, among the above solvent groups, from the viewpoint of the smoothing effect of the surface, MIBK may also be selected.
<聚醯胺酸之原料> <raw material of polyamide>
聚醯胺酸通常由四羧酸二酐成分與二胺成分合成。 Polyamic acid is usually synthesized from a tetracarboxylic dianhydride component and a diamine component.
≪四羧酸二酐成分≫ ≪Tetracarboxylic dianhydride component≫
四羧酸二酐並無特別限制，但較佳為芳香族四羧酸二酐。例如，作為四羧酸二酐，可列舉3,3',4,4'-二苯甲酮四羧酸二酐、2,3,3',4'-聯苯四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、4,4'-氧二鄰苯二甲酸酐、9,9-雙(3,4-二羧基苯基)茀二酐、9,9'-雙[4-(3,4-二羧基苯氧基)苯基]茀二酐、3,3',4,4'-聯苯醚四碳酸二酐、2,3,5,6-吡啶四羧酸二酐、3,4,9,10-苝四羧酸二酐、4,4'-磺醯基二鄰苯二甲酸二酐、對聯三苯-3,4,3',4'-四羧酸二酐、間聯三苯-3,3',4,4'-四羧酸二酐、3,3',4,4'-二苯醚四羧酸二酐等，或者3,3',4,4'-聯苯四羧酸二酐(以下，有時亦簡稱為BPDA)。 The tetracarboxylic dianhydride is not particularly limited, but it is preferably an aromatic tetracarboxylic dianhydride. For example, examples of the tetracarboxylic dianhydride include 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 3 ,3',4,4'-diphenylbenzene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1 ,2,5,6-Naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl) stilbene dianhydride, 9,9' -Bis[4-(3,4-dicarboxyphenoxy)phenyl] stilbene dianhydride, 3,3',4,4'-biphenyl ether tetracarbonic dianhydride, 2,3,5,6-pyridine Tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyl diphthalic dianhydride, terphenyl-3,4,3',4' -Tetracarboxylic dianhydride, metatriphenyl-3,3',4,4'-tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, etc., or 3 ,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter, sometimes also referred to as BPDA).
再者，於上述四羧酸二酐之芳香環上亦可具有經烷基取代及鹵素取代之至少一種取代之部位。又，作為上述芳香族四羧酸二酐，亦可使用複數種四羧酸二酐。 In addition, the aromatic ring of the tetracarboxylic dianhydride may have at least one kind of substituted portion substituted with alkyl and halogen. In addition, as the above-mentioned aromatic tetracarboxylic dianhydride, plural kinds of tetracarboxylic dianhydride can also be used.
又，為了獲得具備具有低熱膨脹特性之聚醯亞胺層之聚醯亞胺積層體(關於構造將於後文進行敍述)，較佳為將BPDA及均苯四甲酸酐之至少一者作為主成分，尤佳為使用具有剛性結構之BPDA。再者，聚醯胺酸中之全部四羧酸二酐成分(即，構成聚醯胺酸之四羧酸二酐)之中，較佳為使用50%以上之BPDA，更佳為使用70%以上，進而較佳為使用90%以上。 In addition, in order to obtain a polyimide laminate having a polyimide layer having low thermal expansion characteristics (the structure will be described later), it is preferable to use at least one of BPDA and pyromellitic anhydride as the main Ingredients, particularly preferred is the use of BPDA with a rigid structure. Furthermore, among all the tetracarboxylic dianhydride components in the polyamic acid (that is, the tetracarboxylic dianhydride constituting the polyamic acid), it is preferable to use 50% or more of BPDA, and more preferably 70% Above, further preferably 90% or more is used.
≪二胺成分≫ ≪Diamine component≫
二胺成分並無特別限制，例如可列舉4,4'-二胺基二苯醚、3,4'-二胺基二苯醚、4,4，-二胺基二苯基碸、1,5-(4-胺基苯氧基)戊烷、1,3-雙(4-胺基苯氧基)-2,2-二甲基丙烷、2,2-雙(4-胺基苯氧基苯基)丙烷、雙[4-(4-胺基苯氧基)苯基]碸及雙[4-(3-胺基苯氧基)苯基]碸、9,9-雙(胺基苯基)茀、對苯二胺、或者1,4-環己烷二胺等。 The diamine component is not particularly limited, and examples include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4,-diaminodiphenyl sulfone, 1, 5-(4-aminophenoxy)pentane, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 2,2-bis(4-aminophenoxy) Phenylphenyl)propane, bis[4-(4-aminophenoxy)phenyl] phenanthrene and bis[4-(3-aminophenoxy)phenyl] phenanthrene, 9,9-bis(amino Phenyl) stilbene, p-phenylenediamine, or 1,4-cyclohexanediamine, etc.
又，亦可使用複數種二胺。於該情形時，就降低熱膨脹之觀點而言，較佳為使用具有剛性之結構之對苯二胺及1,4-環己烷二胺之至少一者。再者，聚醯胺酸中之全部二胺成分(即，構成聚醯胺酸之二胺)中，較佳為使用對苯二胺及1,4-環己烷二胺之至少一者之50%以上，更佳為使用70%以上，進而較佳為使用90%以上。又，亦可上述構成聚醯胺酸之二胺中之50%以上選自對苯二胺及1,4-環己烷二胺。 Also, plural kinds of diamines can be used. In this case, from the viewpoint of reducing thermal expansion, it is preferable to use at least one of p-phenylenediamine and 1,4-cyclohexanediamine having a rigid structure. Furthermore, it is preferable to use at least one of p-phenylenediamine and 1,4-cyclohexanediamine among all the diamine components in the polyamide (ie, the diamine constituting the polyamide). 50% or more, more preferably 70% or more, and still more preferably 90% or more. Moreover, more than 50% of the diamines constituting the polyamic acid may be selected from p-phenylenediamine and 1,4-cyclohexanediamine.
<聚醯胺酸之聚合方法> <Polyamide acid polymerization method>
聚醯胺酸可使用上述之溶劑及原料藉由通常所知之聚合方法獲得。四羧酸酐與二胺之比率及聚醯胺酸末端並無特別限制。 Polyamide can be obtained by a generally known polymerization method using the above-mentioned solvents and raw materials. The ratio of tetracarboxylic anhydride to diamine and the terminal of polyamic acid are not particularly limited.
再者，於聚醯胺酸保管時要求較高之穩定性之情形時，較佳為提高聚醯胺酸末端由胺基所占之比率。即，四羧酸二酐之總莫耳數除以二胺之總莫耳數之莫耳比較佳為0.980以上且未達1.000，更佳為0.995以上且0.998以下。 Furthermore, when higher stability is required during storage of the polyamic acid, it is preferable to increase the ratio of the amino terminal of the polyamic acid terminal. That is, the total number of moles of tetracarboxylic dianhydride divided by the total number of moles of diamine is preferably 0.980 or more and less than 1.000, more preferably 0.995 or more and 0.998 or less.
其原因在於，藉由將四羧酸二酐之總莫耳數除以二胺之總莫耳 數之莫耳比設為未達1.000，聚醯胺酸末端由胺基所占之比率相較於由酸酐基所占之比率變高，其結果為聚醯胺酸之儲存穩定性改善。 The reason is that by dividing the total moles of tetracarboxylic dianhydride by the total moles of diamine When the molar ratio of the number is less than 1.000, the ratio of the amino terminal of the polyamic acid terminal is higher than that of the acid anhydride group. As a result, the storage stability of the polyamic acid is improved.
又，為了獲得強韌之聚醯亞胺層，較佳為使四羧酸二酐之總莫耳數除以二胺之總莫耳數之莫耳比接近於1.000，充分提高分子量。例如，若四羧酸二酐之總莫耳數除以二胺之總莫耳數之莫耳比為0.980以上，則可獲得堅固之聚醯亞胺層。 In addition, in order to obtain a tough polyimide layer, it is preferable to make the molar ratio of the total molar number of tetracarboxylic dianhydride divided by the total molar number of diamines close to 1.000 to sufficiently increase the molecular weight. For example, if the molar ratio of the total moles of tetracarboxylic dianhydride divided by the total moles of diamine is 0.980 or more, a strong polyimide layer can be obtained.
且說，用於聚合之反應裝置較佳為具備用於控制反應溫度之溫度調節裝置。並且，作為使聚醯胺酸聚合之情形之反應溫度，較佳為0℃以上且80℃以下。尤其是，若反應溫度為20℃以上且60℃以下，則抑制作為聚合之逆反應之醯胺鍵之解離，並且聚醯胺酸之生成反應易於進行，黏度易於上升，故而進而較佳。 In addition, the reaction device for polymerization is preferably equipped with a temperature adjustment device for controlling the reaction temperature. In addition, the reaction temperature in the case of polymerizing polyamic acid is preferably 0°C or higher and 80°C or lower. In particular, if the reaction temperature is 20° C. or more and 60° C. or less, the dissociation of the amide bond which is the reverse reaction of polymerization is suppressed, and the formation reaction of the polyamic acid is easy to proceed, and the viscosity tends to increase, which is more preferable.
又，於聚合後，以黏度、即分子量調整為目的，亦可以70~90℃左右進行1~24小時之加熱處理。加熱處理係先前被稱作蒸煮(cooking)之操作。藉由進行該加熱處理，能夠促進聚醯胺酸之解離、及因與體系中之水之反應所導致之酸酐之失活，將聚醯胺酸溶液之分子量調整至所需之值。 In addition, after the polymerization, for the purpose of adjusting the viscosity, that is, the molecular weight, heat treatment may be performed at about 70 to 90°C for 1 to 24 hours. Heat treatment is an operation previously known as cooking. By performing this heat treatment, the dissociation of the polyamic acid and the deactivation of the acid anhydride caused by the reaction with the water in the system can be promoted, and the molecular weight of the polyamic acid solution can be adjusted to a desired value.
又，因加熱處理而未反應之四羧酸二酐變得容易失活。因此，較佳為將聚合反應與蒸煮分開進行。然而，亦可自最初將反應溫度設為70~90℃，一次性進行聚合反應與蒸煮。 In addition, unreacted tetracarboxylic dianhydride due to heat treatment becomes easily deactivated. Therefore, it is preferable to separate the polymerization reaction from the cooking. However, it is also possible to set the reaction temperature from 70 to 90°C from the beginning to perform the polymerization reaction and cooking at once.
再者，於聚醯胺酸之聚合時溶解之聚醯胺酸之固形物成分濃度為5~30重量%，較佳為8~25重量%，進而較佳為10~20重量%。其原因在於，若成為此種固形物成分濃度，則可抑制由未溶解原料之異常聚合所引起之凝膠化，而且聚醯胺酸之生成反應易於進行。 Furthermore, the solid component concentration of the polyamic acid dissolved during the polymerization of polyamic acid is 5 to 30% by weight, preferably 8 to 25% by weight, and more preferably 10 to 20% by weight. The reason for this is that, if such a solid content concentration is used, gelation caused by abnormal polymerization of undissolved raw materials can be suppressed, and the formation reaction of polyamic acid easily proceeds.
<烷氧基矽烷改性聚醯胺酸溶液> <Alkoxysilane modified polyamic acid solution>
作為聚醯胺酸，亦可使用藉由烷氧基矽烷改性之烷氧基矽烷改性聚醯胺酸。若為烷氧基矽烷改性聚醯胺酸，則可獲得聚醯亞胺層與 基板之密接性優異之聚醯亞胺積層體。 As the polyamic acid, alkoxysilane-modified polyamic acid modified with alkoxysilane can also be used. If it is alkoxysilane modified polyamic acid, the polyimide layer and Polyimide laminate with excellent substrate adhesion.
此處，對烷氧基矽烷改性聚醯胺酸進行說明。烷氧基矽烷改性聚醯胺酸係藉由使含有胺基之烷氧基矽烷化合物與聚醯胺酸於溶液中進行反應而獲得。 Here, the alkoxysilane-modified polyamide will be described. The alkoxysilane-modified polyamic acid is obtained by reacting an alkoxysilane compound containing an amine group and a polyamic acid in a solution.
利用具有胺基之烷氧基矽烷化合物之改性係藉由於聚醯胺酸溶解於溶劑而成之聚醯胺酸溶液中添加具有胺基之烷氧基矽烷化合物並使其反應而進行。 The modification using an alkoxysilane compound having an amine group is performed by adding and reacting an alkoxysilane compound having an amine group in a polyamic acid solution in which a polyamic acid is dissolved in a solvent.
作為具有胺基之烷氧基矽烷化合物，可列舉3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、3-(2-胺基乙基)胺基丙基三甲氧基矽烷、3-苯基胺基丙基三甲氧基矽烷、2-胺基苯基三甲氧基矽烷、或3-胺基苯基三甲氧基矽烷等。 Examples of the alkoxysilane compound having an amine group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyl diethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 2-amino Phenyltrimethoxysilane, or 3-aminophenyltrimethoxysilane, etc.
該等烷氧基矽烷化合物相對於聚醯胺酸100重量份之調配比率較佳為0.01~0.50重量份，更佳為0.01~0.10重量份，進而較佳為0.01~0.05重量份。 The compounding ratio of the alkoxysilane compounds to 100 parts by weight of the polyamic acid is preferably 0.01 to 0.50 parts by weight, more preferably 0.01 to 0.10 parts by weight, and still more preferably 0.01 to 0.05 parts by weight.
若烷氧基矽烷化合物之調配比率為0.01重量份以上，則於聚醯亞胺積層體中，可充分發揮抑制聚醯亞胺層自無機基板剝離之效果。又，若烷氧基矽烷化合物之調配比率為0.50重量份以下，則可充分確保聚醯胺酸之分子量，因此聚醯亞胺層不會產生脆化等問題。 If the compounding ratio of the alkoxysilane compound is 0.01 parts by weight or more, in the polyimide laminate, the effect of suppressing the peeling of the polyimide layer from the inorganic substrate can be sufficiently exerted. In addition, if the compounding ratio of the alkoxysilane compound is 0.50 parts by weight or less, the molecular weight of the polyamic acid can be sufficiently ensured, so the polyimide layer does not cause problems such as embrittlement.
但是，若於將末端之大部分設為胺基之聚醯胺酸中添加含有胺基之烷氧基矽烷化合物，則聚醯胺酸溶液之黏度下降。對此，發明者等人推測其原因在於，藉由聚醯胺酸中之醯胺鍵解離之時再生之酸二酐基與烷氧基矽烷化合物之胺基進行反應，而進行改性反應，並且聚醯胺酸之分子量降低。 However, if an alkoxysilane compound containing an amine group is added to a polyamic acid having most of its terminals as an amine group, the viscosity of the polyamic acid solution decreases. In this regard, the inventors speculated that the reason is that the acid dianhydride group regenerated at the time of dissociation of the amide bond in the polyamic acid reacts with the amine group of the alkoxysilane compound to perform the modification reaction, And the molecular weight of polyamide decreases.
再者，為了抑制酸二酐基與水之反應且使烷氧基矽烷改性反應易於進行，反應溫度較佳為0℃以上且80℃以下，更佳為20℃以上且 60℃以下。 Furthermore, in order to suppress the reaction of the acid dianhydride group with water and to facilitate the alkoxysilane modification reaction, the reaction temperature is preferably 0°C or more and 80°C or less, more preferably 20°C or more and Below 60℃.
<關於聚醯胺酸溶液之黏度> <About the viscosity of polyamide solution>
又，聚醯胺酸溶液之黏度較佳為1.0Pa．s以上且20.0Pa．s以下，更佳為1.5Pa．s以上且15.0Pa．s以下，進而較佳為2.0Pa．s以上且10.0Pa．s以下。 Also, the viscosity of the polyamide solution is preferably 1.0Pa. s above and 20.0Pa. Below s, more preferably 1.5Pa. s above and 15.0Pa. s or less, and further preferably 2.0Pa. s above and 10.0Pa. s below.
若聚醯胺酸溶液之黏度為1.0Pa．s以上，則可確保充分之膜厚精度。又，若聚醯胺酸溶液之黏度為20.0Pa．s以下，則可抑制凝膠化，用於去除異物之過濾步驟所需之時間變短，生產性亦變得良好。藉由將聚醯胺酸溶液之黏度設為15.0Pa．s以下，能夠進一步提高生產性。 If the viscosity of the polyamic acid solution is 1.0Pa. Above s, sufficient film thickness accuracy can be ensured. Also, if the viscosity of the polyamic acid solution is 20.0Pa. Below s, gelation can be suppressed, the time required for the filtering step for removing foreign materials becomes shorter, and the productivity becomes good. By setting the viscosity of the polyamide solution to 15.0Pa. Below s, productivity can be further improved.
再者，黏度之測定條件係使用黏度計RE-215/U(東機產業股份有限公司製造)，藉由JIS K7117-2：1999中所記載之方法測定黏度。將附帶之恆溫槽設定為23.0℃，測定溫度以始終固定之方式進行調整。 In addition, the measurement conditions of viscosity are using the viscosity meter RE-215/U (made by Toki Industries Co., Ltd.), and the viscosity is measured by the method described in JIS K7117-2:1999. Set the attached thermostat to 23.0°C, and adjust the measurement temperature in a way that is always fixed.
<對聚醯胺酸溶液之加工特性或各種功能性之賦予> <Attachment of the processing characteristics or various functionalities of the polyamic acid solution>
針對聚醯胺酸溶液，為了賦予加工特性或各種功能性，亦可調配其他各種有機或無機之低分子化合物，或者有機或無機之高分子化合物。 For the polyamic acid solution, in order to impart processing characteristics or various functionalities, various other organic or inorganic low molecular compounds or organic or inorganic high molecular compounds can also be formulated.
例如，可使用染料、塑化劑、無機微粒子及/或增感劑等。作為無機微粒子，可列舉微粒子狀之二氧化矽(氧化矽)粉末或氧化鋁粉末等無機氧化物粉末，或者微粒子狀之碳酸鈣粉末或磷酸鈣粉末等無機鹽粉末。然而，該等無機微粒子之粗大粒子有可能會成為於下一步驟以後之缺陷之原因。因此，該等無機微粒子較佳為均勻分散。又，該等無機微粒子亦可為多孔質或中空結構。並且，作為無機微粒子之功能，可列舉顏料或填料等。又，其形態可為纖維等。 For example, dyes, plasticizers, inorganic fine particles, and/or sensitizers can be used. Examples of the inorganic fine particles include inorganic oxide powders such as particulate silicon dioxide (silica) powder and alumina powder, or inorganic salt powders such as particulate calcium carbonate powder and calcium phosphate powder. However, the coarse particles of these inorganic fine particles may be the cause of defects after the next step. Therefore, the inorganic fine particles are preferably uniformly dispersed. In addition, the inorganic fine particles may have a porous or hollow structure. In addition, as the function of the inorganic fine particles, pigments and fillers may be mentioned. Also, the form may be fiber or the like.
<聚醯胺酸溶液之後處理> <Post-processing of Polyamic Acid Solution>
於以上述方式獲得之聚醯胺酸溶液中，視需要為了減少異物而 實施過濾處理。 In the polyamic acid solution obtained in the above manner, if necessary, in order to reduce foreign matter, Implement filtration.
用於過濾之過濾器只要為過濾之溶液不侵蝕過濾器之材質者，則無特別限制，適當地選擇合適之過濾器材料即可。過濾器孔徑可根據目的而選擇，並無特別限制，較佳為0.01μm~3μm，進而較佳為0.1μm~1μm。再者，視需要，可重複實施過濾，亦可組合2種以上之過濾器實施多段過濾。 The filter used for filtration is not particularly limited as long as the filtered solution does not erode the filter material, and an appropriate filter material may be appropriately selected. The filter pore size can be selected according to the purpose and is not particularly limited, but is preferably 0.01 μm to 3 μm, and more preferably 0.1 μm to 1 μm. Furthermore, if necessary, the filtration may be repeated, or two or more filters may be combined to perform multi-stage filtration.
並且，藉由過濾聚醯胺酸溶液，而使聚醯胺酸溶液中之異物減少，從而獲得異物較少之聚醯亞胺積層體。再者，作為聚醯胺酸溶液中之異物之個數，使用光散射式液中粒子計數器(詳細之測定裝置將於後文進行敍述)而測得之值較佳為0.5μm以上之異物為100個/g以下，更佳為50個/g以下。 Furthermore, by filtering the polyamic acid solution, the foreign matters in the polyamic acid solution are reduced, thereby obtaining a polyimide laminate with less foreign matters. In addition, as the number of foreign matters in the polyamic acid solution, a light scattering liquid particle counter (detailed measurement device will be described later) and the measured value is preferably 0.5 μm or more foreign matter is 100 pieces/g or less, more preferably 50 pieces/g or less.
<關於聚醯胺酸溶液之水分> <About the Moisture of Polyamic Acid Solution>
上述之聚醯胺溶液中之水分可藉由容量滴定卡氏水分計進行測定(詳細之測定裝置及測定條件將於後文進行敍述)。聚醯胺酸溶液中之水分較佳為500ppm以上且3000ppm以下。若水分為3000ppm以下，則可充分發揮利用莫耳比之調整所得之儲存穩定性提高之效果，故而較佳。進而若為1000ppm以下，則可降低因聚醯胺酸分子中之醯胺鍵之分解而產生之酸二酐基與水反應而失活之概率，抑制保管時之黏度變化，故而更佳。溶液中之水分可分為來自原料及來自作業環境。雖然有各種用以減少水分之方法，但使用多餘之步驟或過量之設備將水分減少所需以上亦會導致成本提高，故而欠佳。例如，由於市售之醯胺系溶劑之水分為500ppm左右，故而將水分減少至其以下會伴隨著成本提高，故而欠佳。 The moisture in the above-mentioned polyamide solution can be measured by a volumetric titration Karl Fischer moisture meter (detailed measurement device and measurement conditions will be described later). The moisture in the polyamic acid solution is preferably 500 ppm or more and 3000 ppm or less. If the moisture content is 3000 ppm or less, the effect of improving the storage stability by adjusting the molar ratio can be fully exerted, which is preferable. Furthermore, if it is 1000 ppm or less, the probability of the acid dianhydride group generated by the decomposition of the amide bond in the polyamide molecule reacting with water to be deactivated is reduced, and the change in viscosity during storage is suppressed, which is more preferable. The water in the solution can be divided into raw materials and operating environment. Although there are various methods for reducing moisture, the use of extra steps or excessive equipment to reduce the moisture required above will also lead to increased costs, so it is not good. For example, since the water content of commercially available amide-based solvents is about 500 ppm, reducing the water content below this level is accompanied by an increase in cost, which is undesirable.
作為減少水分之方法，有效的是嚴格進行原料之保管而避免水分之混入，利用乾燥空氣或乾燥氮氣等置換反應環境。進而亦可於減壓下進行處理。 As a method of reducing moisture, it is effective to strictly store raw materials to avoid mixing of moisture, and replace the reaction environment with dry air or dry nitrogen. Furthermore, the treatment can be performed under reduced pressure.
<聚醯亞胺積層體之製造方法> <Manufacturing method of polyimide laminate>
具備聚醯亞胺層及基板之積層體(例如，包含聚醯亞胺層及基板之積層體)係藉由將上述之聚醯胺酸溶液流延(塗佈)於基板上並進行加熱使其醯亞胺化而製造。 A laminate having a polyimide layer and a substrate (for example, a laminate including a polyimide layer and a substrate) is obtained by casting (coating) the above-mentioned polyamic acid solution on the substrate and heating It is manufactured by imidization.
再者，此處之基板意指支持體。具體而言，可列舉玻璃基板或各種金屬基板，較佳為使用玻璃基板。作為玻璃基板，使用鈉鈣玻璃、硼矽酸玻璃、或無鹼玻璃等。尤其是，於薄膜電晶體之製造步驟中，由於通常使用無鹼玻璃，故而作為基板更佳為無鹼玻璃。 Furthermore, the substrate here means a support. Specifically, a glass substrate or various metal substrates may be mentioned, and a glass substrate is preferably used. As the glass substrate, soda lime glass, borosilicate glass, or alkali-free glass is used. In particular, in the manufacturing process of the thin film transistor, since alkali-free glass is generally used, the substrate is more preferably alkali-free glass.
作為用於聚醯亞胺積層體之基板之厚度，較佳為0.4~5.0mm。若基板為0.4mm以上，則基板之操作變得容易，故而較佳。又，若基板為5.0mm以下，則基板之熱容量不會變大，於加熱步驟及/或冷卻步驟之生產性提高，故而較佳。 The thickness of the substrate used for the polyimide laminate is preferably 0.4 to 5.0 mm. If the substrate is 0.4 mm or more, the operation of the substrate becomes easy, which is preferable. In addition, if the substrate is 5.0 mm or less, the thermal capacity of the substrate does not increase, and the productivity in the heating step and/or cooling step is improved, which is preferable.
作為聚醯胺酸溶液於基板上之流延方法，可使用公知之方法。例如，可列舉凹版塗佈法、旋轉塗佈法、絲網印刷法、浸漬塗佈法、棒式塗佈法、刮塗法、輥塗法、或模具塗佈法等公知之流延方法。 As a method for casting the polyamide solution on the substrate, a known method can be used. For example, a well-known casting method such as a gravure coating method, a spin coating method, a screen printing method, a dip coating method, a bar coating method, a blade coating method, a roll coating method, or a die coating method can be mentioned.
藉由對聚醯胺酸溶液進行加熱使其醯亞胺化而獲得聚醯亞胺積層體之情形之加熱溫度、及加熱時間可適當決定，只要不對特性造成影響，則無特別限制。以下表示一例。 The heating temperature and the heating time in the case of obtaining a polyimide laminate by heating the polyamic acid solution and imidizing it can be appropriately determined, and there is no particular limitation as long as it does not affect the characteristics. An example is shown below.
首先，將烷氧基矽烷改性聚醯胺酸溶液流延於無機基板。並且，較佳為將塗佈有聚醯胺酸之無機基板以60~200℃之溫度加熱(乾燥)3~120分鐘。關於該情形之加熱起始溫度，就提高聚醯亞胺積層體之生產效率之觀點而言，較佳為100℃以上，進而就表現低熱膨脹特性之觀點而言，自110~130℃之溫度開始加熱，該溫度下之加熱時間尤佳為10~60分鐘。又，例如可如以100℃乾燥30分鐘，繼而以120℃乾燥30分鐘般，以2個階段之溫度進行乾燥。 First, the alkoxysilane-modified polyamic acid solution was cast on the inorganic substrate. Furthermore, it is preferable to heat (dry) the inorganic substrate coated with polyamide at a temperature of 60 to 200° C. for 3 to 120 minutes. The heating starting temperature in this case is preferably 100°C or higher from the viewpoint of improving the production efficiency of the polyimide laminate, and further from the viewpoint of exhibiting low thermal expansion characteristics, a temperature from 110 to 130°C Start heating. The heating time at this temperature is preferably 10 to 60 minutes. In addition, for example, it can be dried at a temperature of two stages, such as drying at 100°C for 30 minutes and then at 120°C for 30 minutes.
其次，為了進行醯亞胺化，將上述之塗佈有聚醯胺酸之無機基板於溫度200~500℃下加熱3分鐘~300分鐘。此時較佳為自低溫緩慢地變為高溫並升溫至最高溫度。升溫速度較佳為2℃/分鐘~10℃/分鐘，更佳為4℃/分鐘~10℃/分鐘。 Next, in order to carry out amide imidization, the above-mentioned inorganic substrate coated with polyamide acid is heated at a temperature of 200 to 500° C. for 3 minutes to 300 minutes. In this case, it is preferable to slowly change from a low temperature to a high temperature and increase the temperature to the highest temperature. The heating rate is preferably 2°C/min to 10°C/min, and more preferably 4°C/min to 10°C/min.
又，醯亞胺化中之最高溫度較佳為300~500℃之溫度範圍。若最高溫度為300℃以上，則充分進行熱醯亞胺化，若最高溫度為500℃以下，則可抑制聚醯亞胺之熱劣化。又，達到最高溫度前，亦可以任意之溫度保持任意之時間。加熱環境可為空氣下、減壓下、或者氮氣等惰性氣體中之任一種。又，作為加熱裝置，可使用熱風烘箱、紅外線烘箱、真空烘箱、無氧化烘箱或加熱板等公知之裝置。 In addition, the maximum temperature in the amide imidization is preferably in the temperature range of 300 to 500°C. If the maximum temperature is 300° C. or higher, thermal imidization is sufficiently performed, and if the maximum temperature is 500° C. or lower, thermal deterioration of the polyimide can be suppressed. In addition, it can be kept at any temperature for any time before reaching the maximum temperature. The heating environment may be any of inert gas under air, under reduced pressure, or nitrogen. In addition, as the heating device, a known device such as a hot air oven, an infrared oven, a vacuum oven, a non-oxidation oven, or a heating plate can be used.
<醯亞胺化觸媒> <Amidation Catalyst>
再者，於醯亞胺化之情形時，亦可視需要於聚醯胺酸溶液中加入醯亞胺化觸媒，進而進行加熱。 Furthermore, in the case of amide imidization, an amide imidization catalyst may also be added to the polyamic acid solution as needed, and then heated.
作為醯亞胺化觸媒，較佳為使用三級胺。三級胺進而較佳為雜環式之三級胺。作為雜環式之三級胺之較佳具體例，可列舉吡啶、2,5-二乙基吡啶、甲基吡啶、喹啉、或異喹啉等。 As the amide imidization catalyst, a tertiary amine is preferably used. The tertiary amine is further preferably a heterocyclic tertiary amine. Preferred specific examples of the heterocyclic tertiary amine include pyridine, 2,5-diethylpyridine, picoline, quinoline, and isoquinoline.
醯亞胺化劑之使用量較佳為相對於烷氧基矽烷改性聚醯胺酸之反應部位為0.01~2.00當量，尤佳為0.02~1.20當量。若醯亞胺化觸媒為0.01當量以上，則可充分獲得觸媒之效果。若醯亞胺化觸媒為2.00當量以下，則不參與反應之觸媒之比率較少，故而較佳。 The use amount of the amide imidization agent is preferably 0.01 to 2.00 equivalents, and more preferably 0.02 to 1.20 equivalents relative to the reaction site of the alkoxysilane-modified polyamic acid. If the amide imidization catalyst is 0.01 equivalent or more, the catalyst effect can be fully obtained. If the amide imidization catalyst is less than 2.00 equivalents, the ratio of catalysts that do not participate in the reaction is small, so it is preferable.
<聚醯亞胺層之線膨脹特性> <Linear expansion characteristics of polyimide layer>
聚醯亞胺積層體之聚醯亞胺層具有低線膨脹特性。例如於藉由熱機械分析(TMA：Thermo Mechanical Analysis)測定該等值之情形時，首先，自聚醯亞胺積層體剝離聚醯亞胺層。然後，測定該聚醯亞胺層之膜之膜厚之後，將該膜切割成10mm×3mm之尺寸。然後，針對該切割成之試樣(膜試樣)於其長邊施加負載29.4mN，於氮氣環境 下以10℃/min自20℃暫時升溫至500℃後，冷卻至20℃，進而以10℃/min升溫至500℃。於該過程中，根據第二次升溫時之自100℃至300℃中每單位溫度之試樣之應變之變化量求出線膨脹係數。 The polyimide layer of the polyimide laminate has low linear expansion characteristics. For example, when measuring these values by Thermo Mechanical Analysis (TMA: Thermo Mechanical Analysis), first, the polyimide layer is peeled from the polyimide laminate. Then, after measuring the film thickness of the film of the polyimide layer, the film was cut into a size of 10 mm×3 mm. Then, apply a load of 29.4 mN on the long side of the cut sample (membrane sample) in a nitrogen atmosphere The temperature was temporarily increased from 20°C to 500°C at 10°C/min, then cooled to 20°C, and further increased to 500°C at 10°C/min. In this process, the linear expansion coefficient is determined from the amount of change in strain per unit temperature of the sample from 100°C to 300°C during the second temperature increase.
關於藉由該測定方法求出之線膨脹係數，就具有與無機基板相同之線膨脹係數之觀點而言，較佳為-10ppm/K以上且20ppm/K以下，就與通常用作基板材料之無機玻璃相同之觀點而言，更佳為1ppm/K以上且15ppm/K以下，就與通常用於顯示器用途之無鹼玻璃相同之觀點而言，進而較佳為3ppm/K以上且10ppm/K以下，尤佳為6ppm/K以上且8ppm/K。再者，本說明書中之線膨脹係數係表示藉由上述測定方法所求出之自100℃至300℃之範圍中之線膨脹係數。 The linear expansion coefficient obtained by this measurement method is preferably -10 ppm/K or more and 20 ppm/K or less from the viewpoint of having the same linear expansion coefficient as that of an inorganic substrate, which From the same viewpoint of inorganic glass, it is more preferably 1 ppm/K or more and 15 ppm/K or less, and from the same viewpoint as the alkali-free glass commonly used for display applications, it is more preferably 3 ppm/K or more and 10 ppm/K Below, it is particularly preferably 6 ppm/K or more and 8 ppm/K. In addition, the linear expansion coefficient in this specification means the linear expansion coefficient in the range from 100°C to 300°C determined by the above-mentioned measurement method.
<聚醯亞胺層之膜厚> <Thickness of polyimide layer>
聚醯亞胺層之厚度較佳為5~50μm。若聚醯亞胺層之厚度為5μm以上，則可確保作為基板所需之機械強度。又，若聚醯亞胺層之厚度為50μm以下，則能夠不自然剝離而獲得聚醯亞胺層與基板之積層體。 The thickness of the polyimide layer is preferably 5-50 μm. If the thickness of the polyimide layer is 5 μm or more, the mechanical strength required for the substrate can be ensured. In addition, if the thickness of the polyimide layer is 50 μm or less, a laminate of the polyimide layer and the substrate can be obtained without natural peeling.
<聚醯亞胺積層體之特性例> <Characteristics of polyimide laminate>
以如上方式獲得之聚醯亞胺積層體之儲存穩定性及製程匹配性優異，可較佳地用於基於公知之利用液晶面板用薄膜電晶體製程之軟性裝置之製造。 The polyimide laminate obtained in the above manner is excellent in storage stability and process matching, and can be preferably used in the manufacture of soft devices based on the well-known thin film transistor process for liquid crystal panels.
例如，於將烷氧基矽烷改性聚醯胺酸溶液流延於無鹼玻璃基板上並進行加熱使其醯亞胺化之情形時，進而若聚醯胺酸骨架選擇特定之結構，則可獲得具備線膨脹係數為-10ppm/K以上且20ppm/K以下之聚醯亞胺層及無鹼玻璃基板之積層體。並且，藉由使用該積層體，可獲得具有優異特性之軟性裝置。 For example, in the case where the alkoxysilane-modified polyamic acid solution is cast on an alkali-free glass substrate and heated to imidize it, and if the polyamic acid skeleton is selected for a specific structure, then A laminate having a polyimide layer having a linear expansion coefficient of -10 ppm/K or more and 20 ppm/K or less and an alkali-free glass substrate is obtained. Furthermore, by using this laminate, a soft device having excellent characteristics can be obtained.
又，由聚醯胺酸溶液製造之聚醯亞胺積層體之聚醯亞胺層與基板之密接性優異。於聚醯亞胺積層體中，聚醯亞胺層與基板之密接性 可以90°剝離強度進行評估。 In addition, the polyimide layer of the polyimide laminate produced from the polyamic acid solution is excellent in adhesion between the polyimide layer and the substrate. In the polyimide laminate, the adhesion between the polyimide layer and the substrate The 90° peel strength can be evaluated.
再者，剝離強度之測定方法係依據ASTM D1876-01標準(關於詳細內容將於後文進行敍述)。並且，剝離強度較佳為0.15N/cm以上。若剝離強度為0.15N/cm以上，則能夠抑制電子元件形成時之剝離。 In addition, the measurement method of peel strength is based on ASTM D1876-01 standard (details will be described later). In addition, the peel strength is preferably 0.15 N/cm or more. If the peel strength is 0.15 N/cm or more, peeling at the time of formation of an electronic component can be suppressed.
藉由使用如以上之聚醯亞胺積層體，可獲得具有優異特性之軟性顯示器基板。即，於聚醯亞胺積層體之聚醯亞胺層上形成電子元件，其後將該聚醯亞胺層自基板剝離，藉此獲得軟性顯示器基板。 By using the polyimide laminate as described above, a flexible display substrate having excellent characteristics can be obtained. That is, an electronic component is formed on the polyimide layer of the polyimide laminate, and then the polyimide layer is peeled from the substrate, thereby obtaining a flexible display substrate.
作為軟性顯示器基板，例如可列舉TFT(Thin Film Transistor，薄膜電晶體)基板、ITO(Indium Tin Oxide，氧化銦錫)等透明導電膜基板、或太陽電池基板等。自基板剝離聚醯亞胺層之方法可使用公知之方法。例如，可用手剝離，亦可使用驅動輥或機械手等機械裝置進行剝離。進而，亦可為於基板與聚醯亞胺層之間設置剝離層之方法。又，例如亦可列舉：藉由於具有大量溝槽之基板上形成氧化矽膜並使蝕刻液浸潤而進行剝離之方法、或者於基板上設置非晶矽層並藉由雷射光使其分離之方法。 Examples of the flexible display substrate include a TFT (Thin Film Transistor) substrate, a transparent conductive film substrate such as ITO (Indium Tin Oxide), or a solar cell substrate. As a method for peeling the polyimide layer from the substrate, a known method can be used. For example, it can be peeled off by hand, or a mechanical device such as a driving roller or a robot can be used for peeling. Furthermore, it may be a method of providing a peeling layer between the substrate and the polyimide layer. In addition, for example, a method of forming a silicon oxide film on a substrate with a large number of trenches and immersing the etching solution for peeling, or a method of providing an amorphous silicon layer on the substrate and separating it by laser light .
進而，軟性顯示器基板可用於有機EL顯示器、液晶顯示器、電子紙、或觸控面板等電子裝置(軟性裝置)。 Furthermore, the flexible display substrate can be used for electronic devices (flexible devices) such as organic EL displays, liquid crystal displays, electronic paper, or touch panels.
再者，關於以上之具備聚醯亞胺層及基板之聚醯亞胺積層體之製造方法及其利用，亦可以如下方式表現。 In addition, the manufacturing method of the above-mentioned polyimide laminate provided with a polyimide layer and a substrate and its use can also be expressed as follows.
於聚醯亞胺積層體之製造方法中，包括將含有由四羧酸二酐與二胺合成之聚醯胺酸及溶劑之聚醯胺酸溶液塗佈於基板上而於該基板上形成聚醯亞胺層之步驟。 In the method for manufacturing a polyimide laminate, it includes applying a polyamic acid solution containing a polyamic acid synthesized from tetracarboxylic dianhydride and diamine and a solvent on a substrate to form a poly on the substrate Steps for the amide imide layer.
並且，聚醯胺酸溶液中所含之溶劑包含選自由4-甲基-2-戊酮、環己酮、四氫呋喃、及二甲苯所組成之溶劑群A中之至少一種、及N- 甲基-2-吡咯啶酮。進而，上述聚醯胺酸溶液之黏度為1.0Pa．s以上且20.0Pa．s以下。 In addition, the solvent contained in the polyamic acid solution includes at least one selected from the solvent group A consisting of 4-methyl-2-pentanone, cyclohexanone, tetrahydrofuran, and xylene, and N- Methyl-2-pyrrolidone. Furthermore, the viscosity of the above-mentioned polyamide solution is 1.0 Pa. s above and 20.0Pa. s below.
又，較佳為上述聚醯胺酸溶液中之聚醯胺酸之固形物成分濃度為10重量%以上且20重量%以下。 Moreover, it is preferable that the solid component concentration of the polyamic acid in the polyamic acid solution is 10% by weight or more and 20% by weight or less.
又，較佳為於聚醯胺酸溶液中所含之溶劑中，選自溶劑群A中之至少一種相對於聚醯胺酸溶液中所含之全部溶劑含有3重量%以上且30重量%以下。 Moreover, it is preferable that the solvent contained in the polyamic acid solution contains at least one kind selected from the solvent group A containing 3% by weight or more and 30% by weight or less with respect to all solvents contained in the polyamic acid solution .
又，較佳為於上述聚醯胺酸溶液中所含之溶劑中，N-甲基-2-吡咯啶酮與溶劑群A所包含之溶劑之重量比為85：15~95：5。 In addition, it is preferable that the weight ratio of N-methyl-2-pyrrolidone to the solvent contained in the solvent group A in the solvent contained in the polyamic acid solution is 85:15 to 95:5.
又，較佳為於上述聚醯胺酸溶液中所含之溶劑中，N-甲基-2-吡咯啶酮與溶劑群A所包含之溶劑之重量比為90：10~95：5。 In addition, it is preferable that the weight ratio of N-methyl-2-pyrrolidone to the solvent contained in the solvent group A in the solvent contained in the polyamic acid solution is 90:10 to 95:5.
又，較佳為選自溶劑群A中之溶劑為4-甲基-2-戊酮。 Moreover, it is preferable that the solvent selected from the solvent group A is 4-methyl-2-pentanone.
又，較佳為聚醯胺酸藉由烷氧基矽烷進行改性。 In addition, it is preferred that the polyamic acid is modified by alkoxysilane.
又，較佳為構成聚醯胺酸之四羧酸二酐中之50%以上為3,3',4,4'-聯苯基四羧酸二酐。 Furthermore, it is preferable that 50% or more of the tetracarboxylic dianhydride constituting the polyamic acid is 3,3',4,4'-biphenyltetracarboxylic dianhydride.
又，較佳為構成上述聚醯胺酸之二胺中之50%以上選自對苯二胺及1,4-環己烷二胺。 Moreover, it is preferable that 50% or more of the diamines constituting the polyamic acid are selected from p-phenylenediamine and 1,4-cyclohexanediamine.
又，較佳為聚醯亞胺積層體之聚醯亞胺層之線膨脹係數為-10ppm/K以上且20ppm/K以下。 Moreover, it is preferable that the linear expansion coefficient of the polyimide layer of the polyimide laminate is -10 ppm/K or more and 20 ppm/K or less.
並且，本發明亦為一種軟性顯示器基板之製造方法，其包括：於利用如上所述之聚醯亞胺積層體之製造方法所獲得之聚醯亞胺積層體中之聚醯亞胺層形成電子元件之步驟；及將形成有該電子元件之聚醯亞胺層自基板剝離之步驟。 Moreover, the present invention is also a method for manufacturing a flexible display substrate, which includes: forming electrons in the polyimide layer in the polyimide laminate obtained by the manufacturing method of the polyimide laminate as described above The step of the component; and the step of peeling the polyimide layer formed with the electronic component from the substrate.
又，本發明亦為一種軟性裝置，其包含利用軟性顯示器基板之製造方法所獲得之軟性顯示器基板。 In addition, the present invention is also a flexible device including a flexible display substrate obtained by a method for manufacturing a flexible display substrate.
本發明並不限制於上述之各實施形態，於請求項所示之範圍內 可進行各種變更，關於適當組合不同之實施形態分別所揭示之技術手段而獲得之實施形態亦包含於本發明之技術範圍內。進而，藉由組合各實施形態分別所揭示之技術手段，可形成新的技術特徵。 The present invention is not limited to the above-mentioned embodiments, within the scope shown in the claims Various changes can be made, and embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the technical scope of the present invention. Furthermore, by combining the technical means disclosed in each embodiment, new technical features can be formed.
以下，基於實施例對本發明具體地進行說明。然而，本發明並不限定於該等實施例，可於不脫離本發明之主旨之範圍內進行實施形態之變更。 Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to these embodiments, and the embodiments can be changed without departing from the scope of the present invention.
根據下述之表1所記載之條件，求出重量平均分子量(Mw)。 The weight average molecular weight (Mw) was determined under the conditions described in Table 1 below.
將預先測定異物量之N-甲基-2-吡咯啶酮於容量為100mL之清潔瓶中計量65g左右，於該清潔瓶中進而計量於實施例中所獲得之各溶液15g左右。藉由攪拌脫泡機(THINKY製造：AR-250)以轉數2000rpm對該清潔瓶進行攪拌3分鐘、脫泡處理27分鐘，調整測定用之稀釋之溶液。 N-methyl-2-pyrrolidone whose amount of foreign matter has been measured in advance is weighed in a clean bottle with a capacity of 100 mL to weigh about 65 g, and in the clean bottle, about 15 g of each solution obtained in the example is further weighed. The cleaned bottle was stirred at 2000 rpm for 3 minutes and defoamed for 27 minutes by a stirring deaerator (manufactured by THINKY: AR-250), and the diluted solution for measurement was adjusted.
藉由光散射式粒子計數器(思百吉公司製造：SL1500，最小可測粒徑：0.2μm)測定該調整之溶液。1次之測定量設為10mL(最初之1 mL廢棄)而實施6次之測定(合計54mL)。根據所獲得之測定值，依據下述式算出每1g溶液中所含之0.5μm以上之異物之個數。 The adjusted solution was measured by a light-scattering particle counter (manufactured by Sibaiji: SL1500, minimum measurable particle size: 0.2 μm). The amount of measurement per time is set to 10mL (the first one mL was discarded) and measured 6 times (total 54 mL). Based on the obtained measurement values, the number of foreign substances of 0.5 μm or more per 1 g of solution was calculated according to the following formula.
每1g溶液中所含之異物之個數=(A-(B×Wb/(Wa+Wb)))/54/(Wa/(Wa+Wb)) Number of foreign substances contained in each 1g of solution = (A-(B×Wb/(Wa+Wb)))/54/(Wa/(Wa+Wb))
但是，式中所使用之符號表示以下之內容。 However, the symbols used in the formula indicate the following.
A：0.5μm以上之異物之個數之測定值 A: The measured value of the number of foreign objects above 0.5μm
B：用於稀釋之N-甲基-2-吡咯啶酮之0.5μm以上之異物之個數之測定值 B: The measured value of the number of foreign substances with a diameter of 0.5 μm or more for diluted N-methyl-2-pyrrolidone
Wa：計量實施例中所獲得之溶液之重量(g) Wa: the weight of the solution obtained in the measurement example (g)
Wb：計量用於稀釋之N-甲基-2-吡咯啶酮之重量(g) Wb: Measure the weight of N-methyl-2-pyrrolidone used for dilution (g)
再者，對於用於本測定之粒子計數器，於使用前依據JIS B9925之標準實施校準。 In addition, the particle counter used for this measurement is calibrated according to the JIS B9925 standard before use.
使用容量滴定卡氏水分計890 Titrando(瑞士萬通日本股份有限公司製造)，藉由JIS K0068之容量滴定法所記載之方法測定烷氧基矽烷改性聚醯胺酸溶液中之水分。其中，將脫水溶劑GEX(三菱化學股份有限公司製造)與N-甲基吡咯啶酮之1：4之混合溶液用作滴定溶劑。 The water content in the alkoxysilane-modified polyamic acid solution was measured by the method described in the volumetric titration method of JIS K0068 using a volumetric Karl Fischer 890 Titrando (manufactured by Metrohm Japan Co., Ltd.). Among them, a 1:4 mixed solution of dehydrating solvent GEX (manufactured by Mitsubishi Chemical Corporation) and N-methylpyrrolidone was used as a titration solvent.
使用黏度計RE-215/U(東機產業股份有限公司製造)，藉由JIS K7117-2：1999所記載之方法測定黏度。將附帶之恆溫槽設定為23.0℃，測定溫度始終固定。 Using a viscometer RE-215/U (manufactured by Toki Industry Co., Ltd.), the viscosity was measured by the method described in JIS K7117-2:1999. Set the attached thermostat to 23.0°C, and the measurement temperature is always fixed.
利用下述之實施例及比較例所記載之方法，製作聚醯亞胺積層體，目視觀察其表面之平滑性，並進行評價。評價基準如以下所示。 Using the method described in the following examples and comparative examples, a polyimide laminate was produced, and the smoothness of the surface was visually observed and evaluated. The evaluation criteria are shown below.
A：於聚醯亞胺層之表面無能以目視觀察到之凹凸 A: On the surface of the polyimide layer, there are no irregularities that can be visually observed
B：於聚醯亞胺層之端部有能以目視確認到之凹凸 B: There are irregularities that can be visually confirmed at the end of the polyimide layer
C：於聚醯亞胺層之端部及端部以外之一部分有能以目視確認之凹凸 C: There are irregularities that can be visually confirmed at the end of the polyimide layer and a part other than the end
D：於聚醯亞胺層之表面整體有能以目視確認到之凹凸 D: The entire surface of the polyimide layer has irregularities that can be visually confirmed
再者，根據本評價方法，若為A或B則表面充分平滑。 In addition, according to this evaluation method, if it is A or B, the surface is sufficiently smooth.
線膨脹係數係使用精工電子奈米科技股份有限公司製造之TMA/SS7100，利用基於拉伸荷重法之熱機械分析進行評價。自實施例之聚醯亞胺積層體剝離聚醯亞胺層，製作10mm×3mm之試樣，於長邊施加29.4mN之負載，以10℃/min自20℃暫時升溫至500℃後，冷卻至20℃，進而以10℃/min升溫至500℃時，第二次升溫時之100℃~300℃之範圍內之每單位溫度之試樣之應變之變化量設為線膨脹係數。 The coefficient of linear expansion was evaluated using TMA/SS7100 manufactured by Seiko Instruments Nano Technology Co., Ltd., and thermomechanical analysis based on the tensile load method. The polyimide layer was peeled off from the polyimide laminate of the examples to prepare a sample of 10 mm × 3 mm, a load of 29.4 mN was applied on the long side, and the temperature was temporarily increased from 20°C to 500°C at 10°C/min, and then cooled When the temperature is raised to 20°C and further increased to 500°C at 10°C/min, the change in strain per unit temperature of the sample in the range of 100°C to 300°C during the second temperature increase is taken as the linear expansion coefficient.
依據ASTM D1876-01標準，藉由截切刀將聚醯亞胺積層體切斷為10mm寬，使用東洋精機公司製造之拉力試驗機(Strograph VES1D)，於23℃ 55%RH條件下，以拉伸速度50mm/min剝離50mm之情形之90°剝離強度之平均值作為剝離強度進行評價。 According to ASTM D1876-01 standard, cut by a cutter polyimide laminate was cut into 10mm width, used in the manufacture of Toyo Seiki Seisaku tensile testing machine (Strograph VES1D), 55% RH conditions at 23 ℃, to The average value of the 90° peel strength in the case of a 50 mm/min peel rate at a tensile speed of 50 mm was evaluated as the peel strength.
<聚醯胺酸溶液之製造> <Manufacture of Polyamic Acid Solution>
於具備附聚四氟乙烯製密封栓之攪拌器、攪拌翼、及氮氣導入管之容積2L之玻璃製可分離式燒瓶中，加入N-甲基-2-吡咯啶酮(以下，有時稱為NMP)850.0g，加入對苯二胺(以下，有時稱為PDA)40.1g、4,4'-二胺基二苯醚(以下，有時稱為ODA)0.6g，將溶液一面於油浴中加熱至50.0℃一面於氮氣環境下攪拌30分鐘。 In a 2 L glass separable flask equipped with a stirrer, stirring wing, and nitrogen introduction tube with a sealing plug made of polytetrafluoroethylene, add N-methyl-2-pyrrolidone (hereinafter sometimes referred to as 850.0g, add 40.1g of p-phenylenediamine (hereinafter sometimes referred to as PDA), 0.6g of 4,4'-diaminodiphenyl ether (hereinafter sometimes referred to as ODA), and place the solution on the side Heat to 50.0°C in an oil bath while stirring under a nitrogen atmosphere for 30 minutes.
確認原料均勻溶解後，加入BPDA109.3g，一面於氮氣環境下攪拌10分鐘，一面將溶液之溫度調整至約90℃直至原料完全溶解。進而 一面以固定之溫度進行加熱，一面持續攪拌而降低黏度，獲得於23℃下顯示黏度190泊之黏稠之聚醯胺酸溶液。 After confirming that the raw materials were uniformly dissolved, 109.3 g of BPDA was added, and the temperature of the solution was adjusted to about 90°C until the raw materials were completely dissolved while stirring for 10 minutes under a nitrogen atmosphere. and then While heating at a fixed temperature while continuously stirring to reduce the viscosity, a viscous polyamic acid solution showing a viscosity of 190 poise at 23°C was obtained.
再者，該聚醯胺酸溶液中之二胺化合物及四羧酸二酐之添加濃度相對於全部反應液為15重量%，四羧酸二酐之總莫耳數除以二胺之總莫耳數之莫耳比為0.995。測定聚醯胺酸之分子量，結果Mw=67000。 Furthermore, the addition concentration of the diamine compound and the tetracarboxylic dianhydride in the polyamic acid solution is 15% by weight relative to the total reaction liquid, and the total moles of tetracarboxylic dianhydride divided by the total mole of diamine The molar ratio of ears is 0.995. The molecular weight of polyamide was determined, and the result was Mw=67000.
<利用烷氧基矽烷化合物之改性> <Modification using alkoxysilane compounds>
將該反應溶液於水浴中迅速冷卻，將溶液之溫度調整為約50℃。其次，加入3-胺基丙基乙氧基矽烷(以下，有時稱為γ-APS)之1%NMP溶液7.5g，攪拌2小時。 The reaction solution was quickly cooled in a water bath, and the temperature of the solution was adjusted to about 50°C. Next, 7.5 g of a 1% NMP solution of 3-aminopropylethoxysilane (hereinafter sometimes referred to as γ-APS) was added and stirred for 2 hours.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為13.0重量%且溶液中之溶劑之比率成為NMP/MIBK=90/10之方式，添加NMP及MIBK進行稀釋，獲得於23℃下顯示黏度為7.3Pa．s且水分為1700ppm之聚醯胺酸溶液。 For the polyamic acid solution obtained in Synthesis Example 1, the NMP and MIBK were added and diluted in such a manner that the solid content concentration became 13.0% by weight and the ratio of the solvent in the solution became NMP/MIBK=90/10. The viscosity at 23°C was 7.3 Pa. s Polyamic acid solution with a moisture content of 1700 ppm.
使用孔徑為0.5μm之過濾器及0.2μm之過濾器對所獲得之聚醯胺酸溶液進行多段過濾。關於異物之評價結果，示於下述表2。 The obtained polyamide solution was subjected to multi-stage filtration using a filter with a pore size of 0.5 μm and a filter with 0.2 μm. The evaluation results of foreign substances are shown in Table 2 below.
<聚醯亞胺積層體之製造> <Manufacture of polyimide laminate>
將所獲得之聚醯胺酸溶液利用棒式塗佈機以乾燥後之厚度成為20μm之方式流延於兩邊150mm、厚度0.7mm之正方形之無鹼玻璃板(康寧公司製造之Eagle XG)上，於熱風烘箱內以120℃乾燥30分鐘。其後，將該無鹼玻璃板於氮氣環境下自20℃以4℃/分鐘升溫至180℃，保持30分鐘，進而以4℃/分鐘升溫至450℃，以450℃加熱10分鐘。藉此，獲得聚醯亞胺層之厚度為20μm之聚醯亞胺積層體。再者，無鹼玻璃板之線膨脹係數為3~4ppm/K。 The obtained polyamic acid solution was cast on a square non-alkali glass plate (Eagle XG manufactured by Corning Co., Ltd.) with 150 mm on both sides and a thickness of 0.7 mm using a bar coater so that the thickness after drying became 20 μm. Dry in a hot air oven at 120°C for 30 minutes. Thereafter, the alkali-free glass plate was heated from 20° C. to 4° C./min to 180° C. in a nitrogen atmosphere for 30 minutes, and further heated to 450° C. at 4° C./min and heated at 450° C. for 10 minutes. With this, a polyimide laminate having a thickness of 20 μm was obtained. Furthermore, the linear expansion coefficient of the alkali-free glass plate is 3 to 4 ppm/K.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為13.0重量%且溶液中之溶劑之比率成為NMP/MIBK=95/5之方式，添加NMP及MIBK進行稀釋，獲得於23℃下顯示黏度為7.3Pa．s且水分為2200ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1同樣之方式獲得聚醯亞胺積層體。 For the polyamic acid solution obtained in Synthesis Example 1, the NMP and MIBK were added and diluted in such a manner that the solid content concentration became 13.0% by weight and the ratio of the solvent in the solution became NMP/MIBK=95/5. The viscosity at 23°C was 7.3 Pa. s Polyamide solution with a moisture content of 2200 ppm. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為11.5重量%且溶液中之溶劑之比率成為NMP/THF=75/25之方式，添加NMP及THF進行稀釋，獲得於23℃下顯示黏度為4.0Pa．s且水分為2000ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1同樣之方式獲得聚醯亞胺積層體。 The polyamic acid solution obtained in Synthesis Example 1 was diluted by adding NMP and THF so that the solid content concentration became 11.5% by weight and the ratio of the solvent in the solution became NMP/THF=75/25. The viscosity at 23℃ is 4.0Pa. s Polyamic acid solution with a moisture content of 2000 ppm. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為13.0重量%且溶液中之溶劑之比率成為NMP/二甲苯=90/10之方式，添加NMP及二甲苯進行稀釋，獲得於23℃下顯示黏度為7.8Pa．s且水分為2500ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1同樣之方式獲得聚醯亞胺積層體。 For the polyamic acid solution obtained in Synthesis Example 1, NMP and xylene were added for dilution so that the solid content concentration became 13.0% by weight and the ratio of the solvent in the solution became NMP/xylene=90/10. Obtained at 23 ℃ shows a viscosity of 7.8Pa. s Polyamic acid solution with a moisture content of 2500 ppm. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為13.0重量%且溶液中之溶劑之比率成為NMP/環己酮=90/10之方式，添加NMP及環己酮進行稀釋，獲得於23℃下顯示黏度為7.0Pa．s且水分為1800ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1同樣之方式獲得聚醯亞胺積層體。 For the polyamic acid solution obtained in Synthesis Example 1, the NMP and cyclohexanone were added in such a manner that the solid content concentration became 13.0% by weight and the solvent ratio in the solution became NMP/cyclohexanone=90/10. Dilute to obtain a viscosity of 7.0Pa at 23℃. s Polyamide solution with a moisture content of 1800 ppm. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
<聚醯胺酸溶液之製造> <Manufacture of Polyamic Acid Solution>
於具備附聚四氟乙烯製密封栓之攪拌器、攪拌翼、及氮氣導入 管之容積2L之玻璃製可分離式燒瓶中，加入NMP 850.0g，加入1,4-環己烷二胺41.4g，將溶液於氮氣環境下攪拌30分鐘。 In the stirrer, stirring wing, and nitrogen introduction with the sealing plug made of polytetrafluoroethylene In a separable flask made of glass with a volume of 2 L, 850.0 g of NMP and 41.4 g of 1,4-cyclohexanediamine were added, and the solution was stirred for 30 minutes under a nitrogen atmosphere.
確認原料均勻溶解後，加入BPDA 103.6g，進而加入9,9-雙(3,4-二羧基苯基)茀二酐5.0g，於氮氣環境下將溶液之溫度調整至約80℃並攪拌30分鐘直至於反應初期生成之鹽開始溶解而開始進行聚合反應。其後冷卻至室溫，進而攪拌5小時，獲得於23℃下顯示黏度為226.0Pa．s之黏稠之聚醯胺酸溶液。 After confirming that the raw materials are uniformly dissolved, add 103.6g of BPDA, and then add 5.0g of 9,9-bis(3,4-dicarboxyphenyl) stilbene dianhydride, adjust the temperature of the solution to about 80°C under a nitrogen atmosphere and stir for 30 Minutes until the salt generated at the beginning of the reaction starts to dissolve and the polymerization reaction starts. After cooling to room temperature, and then stirred for 5 hours, obtained at 23 ℃ showed a viscosity of 226.0Pa. s viscous polyamic acid solution.
再者，該聚醯胺酸溶液中之二胺化合物及四羧酸二酐之添加濃度相對於全部反應液為15重量%，四羧酸二酐之總莫耳數除以二胺之總莫耳數之莫耳比為1.000。測定聚醯胺酸之分子量，結果Mw=64000。 Furthermore, the addition concentration of the diamine compound and the tetracarboxylic dianhydride in the polyamic acid solution is 15% by weight relative to the total reaction liquid, and the total moles of tetracarboxylic dianhydride divided by the total mole of diamine The molar ratio of ears is 1.000. The molecular weight of polyamide was determined, and the result was Mw=64000.
對於合成例2中所獲得之聚醯胺酸溶液，以固形物成分濃度成為9.5重量%且溶液中之溶劑之比率成為NMP/MIBK=90/10之方式，添加NMP及MIBK進行稀釋，獲得於23℃下顯示黏度為7.0Pa．s且水分為1300ppm之聚醯胺酸溶液。 For the polyamic acid solution obtained in Synthesis Example 2, the NMP and MIBK were added and diluted in such a manner that the solid content concentration became 9.5% by weight and the ratio of the solvent in the solution became NMP/MIBK=90/10. The viscosity at 23℃ is 7.0Pa. s Polyamide solution with a moisture content of 1300 ppm.
<聚醯亞胺積層體之製造> <Manufacture of polyimide laminate>
利用棒式塗佈機將所獲得之聚醯胺酸溶液以乾燥後之厚度成為10μm之方式流延於兩邊150mm、厚度0.7mm之正方形之無鹼玻璃板(康寧公司製造之Eagle XG)上，於熱風烘箱內以120℃乾燥20分鐘。其後，將該無鹼玻璃板於氮氣環境下自20℃以5℃/分鐘升溫至350℃，以350℃加熱1小時，獲得聚醯亞胺層之厚度為10μm之聚醯亞胺積層體。 Using a bar coater, the obtained polyamic acid solution was cast on a square alkali-free glass plate (Eagle XG manufactured by Corning Corporation) with a thickness of 0.7 mm on both sides and a thickness of 10 μm after drying. Dry in a hot air oven at 120°C for 20 minutes. After that, the alkali-free glass plate was heated from 20° C. to 5° C./min to 350° C. under a nitrogen atmosphere, and heated at 350° C. for 1 hour to obtain a polyimide laminate having a thickness of 10 μm. .
<聚醯胺酸溶液之製造> <Manufacture of Polyamic Acid Solution>
於具備附聚四氟乙烯製密封栓之攪拌器、攪拌翼、及氮氣導入 管之容積2L之玻璃製可分離式燒瓶中，加入NMP 830.0g，加入PDA 45.4g、ODA 0.7g，將溶液一面於油浴中加熱至50.0℃一面於氮氣環境下攪拌30分鐘。 In the stirrer, stirring wing, and nitrogen introduction with the sealing plug made of polytetrafluoroethylene In a glass separable flask with a volume of 2 L, 830.0 g of NMP, 45.4 g of PDA and 0.7 g of ODA were added, and the solution was stirred for 30 minutes while heating to 50.0°C in an oil bath under nitrogen atmosphere.
確認原料均勻溶解後，加入BPDA 123.9g，一面於氮氣環境下攪拌10分鐘一面將溶液之溫度調整至約90℃直至原料完全溶解。進而一面以固定之溫度進行加熱，一面持續攪拌而降低黏度，獲得於23℃下顯示黏度735泊之黏稠之聚醯胺酸溶液。 After confirming that the raw materials were uniformly dissolved, 123.9 g of BPDA was added, and the temperature of the solution was adjusted to about 90°C until the raw materials were completely dissolved while stirring for 10 minutes under a nitrogen atmosphere. Furthermore, while heating at a fixed temperature, while continuing to stir to reduce the viscosity, a viscous polyamic acid solution showing a viscosity of 735 poise at 23°C was obtained.
再者，該聚醯胺酸溶液中之二胺化合物及四羧酸二酐之添加濃度相對於全部反應液為17重量%，四羧酸二酐之總莫耳數除以二胺之總莫耳數之莫耳比為0.995。測定聚醯胺酸之分子量，結果Mw=70000。 In addition, the addition concentration of the diamine compound and the tetracarboxylic dianhydride in the polyamic acid solution is 17% by weight relative to the total reaction solution, and the total moles of tetracarboxylic dianhydride divided by the total mole of diamine The molar ratio of ears is 0.995. The molecular weight of polyamide was determined, and the result was Mw=70,000.
<利用烷氧基矽烷化合物之改性> <Modification using alkoxysilane compounds>
將該反應溶液於水浴中迅速冷卻，將溶液之溫度調整為約50℃。其次，加入γ-APS之1%NMP溶液8.4g，攪拌2小時。 The reaction solution was quickly cooled in a water bath, and the temperature of the solution was adjusted to about 50°C. Next, 8.4 g of 1% NMP solution of γ-APS was added and stirred for 2 hours.
對於合成例3中所獲得之聚醯胺酸溶液，以固形物成分濃度成為12.8重量%且溶液中之溶劑之比率成為NMP/THF=75/25之方式，添加NMP及MIBK進行稀釋，獲得於23℃下顯示黏度為8.0Pa．s且水分為2500ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1同樣之方式獲得聚醯亞胺積層體。 For the polyamic acid solution obtained in Synthesis Example 3, NMP and MIBK were added for dilution in such a manner that the solid content concentration became 12.8% by weight and the ratio of the solvent in the solution became NMP/THF=75/25. The viscosity at 23°C was 8.0 Pa. s Polyamic acid solution with a moisture content of 2500 ppm. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
對於合成例3中所獲得之聚醯胺酸溶液，以固形物成分濃度成為12.8重量%且溶液中之溶劑之比率成為NMP/THF=75/25之方式，添加NMP及THF進行稀釋，獲得於23℃下顯示黏度為5.6Pa．s且水分為2500ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1同樣之方式獲得聚醯亞胺積層體。 For the polyamic acid solution obtained in Synthesis Example 3, NMP and THF were added for dilution in such a manner that the solid content concentration became 12.8% by weight and the ratio of the solvent in the solution became NMP/THF=75/25. The viscosity at 23°C was 5.6 Pa. s Polyamic acid solution with a moisture content of 2500 ppm. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
對於合成例3中所獲得之聚醯胺酸溶液，以固形物成分濃度成為12.8重量%且溶液中之溶劑之比率成為NMP/二甲苯=75/25之方式，添加NMP及二甲苯進行稀釋，獲得於23℃下顯示黏度為8.1Pa．s且水分為2500ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1同樣之方式獲得聚醯亞胺積層體。 For the polyamic acid solution obtained in Synthesis Example 3, NMP and xylene were added for dilution so that the solid content concentration became 12.8% by weight and the solvent ratio in the solution became NMP/xylene=75/25. Obtained at 23 ℃ shows a viscosity of 8.1Pa. s Polyamic acid solution with a moisture content of 2500 ppm. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
對於合成例3中所獲得之聚醯胺酸溶液，以固形物成分濃度成為12.8重量%且溶液中之溶劑之比率成為NMP/環己酮=75/25之方式，添加NMP及環己酮進行稀釋，獲得於23℃下顯示黏度為8.3Pa．s且水分為2500ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1同樣之方式獲得聚醯亞胺積層體。 For the polyamic acid solution obtained in Synthesis Example 3, NMP and cyclohexanone were added in such a manner that the solid content concentration became 12.8% by weight and the ratio of the solvent in the solution became NMP/cyclohexanone=75/25. Dilute to obtain a viscosity of 8.3 Pa at 23℃. s Polyamic acid solution with a moisture content of 2500 ppm. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
觀察實施例1~10所獲得之積層體，於聚醯亞胺層與無鹼玻璃板之間未觀察到氣泡及隆起，於加熱中無自然剝離之情況。並且，能夠自無鹼玻璃板剝離聚醯亞胺層。再者，關於聚醯亞胺層之表面性之評價，示於表2。 When observing the laminates obtained in Examples 1 to 10, no bubbles and bumps were observed between the polyimide layer and the alkali-free glass plate, and there was no natural peeling during heating. In addition, the polyimide layer can be peeled from the alkali-free glass plate. In addition, the evaluation of the surface properties of the polyimide layer is shown in Table 2.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為13.0重量%之方式，加入NMP進行稀釋，獲得於23℃下顯示黏度為7.0Pa．s且水分為1900ppm之聚醯胺酸溶液。 The polyamic acid solution obtained in Synthesis Example 1 was diluted with NMP in such a manner that the solid content concentration became 13.0% by weight to obtain a viscosity of 7.0 Pa at 23°C. s Polyamide solution with a moisture content of 1900 ppm.
對所獲得之聚醯胺酸溶液，使用孔徑為0.5μm之過濾器及0.2μm之過濾器進行多段過濾。關於異物之評價結果，示於表2。 The obtained polyamic acid solution was filtered in multiple stages using a filter with a pore size of 0.5 μm and a filter with 0.2 μm. The evaluation results of foreign materials are shown in Table 2.
以與實施例1相同之方式由過濾後之聚醯胺酸溶液製造聚醯亞胺積層體。然而，將該聚醯胺酸溶液塗佈於無鹼玻璃板後，於熱風烘箱內以120℃乾燥30分鐘時，於膜表面形成有橘皮狀之凹凸。 In the same manner as in Example 1, a polyimide laminate was produced from the filtered polyamic acid solution. However, after coating the polyamic acid solution on an alkali-free glass plate and drying it at 120°C for 30 minutes in a hot air oven, orange peel-like irregularities were formed on the film surface.
其後，於氮氣環境下自20℃以4℃/分鐘升溫至180℃，保持30分鐘，進而以4℃/分鐘升溫至450℃，以450℃加熱10分鐘，獲得聚醯亞胺層之厚度為20μm之聚醯亞胺積層體。 Thereafter, the temperature was raised from 20°C at 4°C/min to 180°C for 30 minutes under a nitrogen atmosphere, and further heated to 450°C at 4°C/min and heated at 450°C for 10 minutes to obtain the thickness of the polyimide layer It is a 20 μm polyimide laminate.
不稀釋合成例1中所獲得之聚醯胺酸溶液，以與實施例1同樣之方式製造聚醯亞胺積層體(再者，聚醯胺酸溶液之黏度於23℃下為13.5Pa．s)。然而，將該聚醯胺酸溶液塗佈於無鹼玻璃板後，於熱風烘箱內以120℃乾燥30分鐘時，於膜表面形成有橘皮狀之凹凸。其後，與比較例1同樣地獲得聚醯亞胺層之厚度為20μm之聚醯亞胺積層體。 Without diluting the polyamic acid solution obtained in Synthesis Example 1, a polyimide laminate was produced in the same manner as in Example 1 (again, the viscosity of the polyamic acid solution at 23°C was 13.5 Pa·s ). However, after coating the polyamic acid solution on an alkali-free glass plate and drying it at 120°C for 30 minutes in a hot air oven, orange peel-like irregularities were formed on the film surface. Thereafter, as in Comparative Example 1, a polyimide laminate having a thickness of 20 μm was obtained.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為11.2重量%且溶液中之溶劑之比率成為NMP/丙二醇單甲醚乙酸酯=90/10之方式，添加NMP及丙二醇單甲醚乙酸酯進行稀釋，獲得於23℃下顯示黏度為7.5Pa．s且水分為2000ppm之聚醯胺酸溶液。 For the polyamic acid solution obtained in Synthesis Example 1, the NMP and NMP were added in such a manner that the solid content concentration became 11.2% by weight and the solvent ratio in the solution became NMP/propylene glycol monomethyl ether acetate=90/10. Propylene glycol monomethyl ether acetate was diluted to obtain a viscosity of 7.5 Pa at 23 °C. s Polyamic acid solution with a moisture content of 2000 ppm.
與實施例1同樣地由所獲得之聚醯胺酸溶液製造聚醯亞胺積層體。然而，將該聚醯胺酸溶液塗佈於無鹼玻璃板後，於熱風烘箱內以120℃乾燥30分鐘，結果於膜表面形成有橘皮狀之凹凸。其後，與比較例1同樣地，獲得聚醯亞胺層之厚度為20μm之聚醯亞胺積層體。 In the same manner as in Example 1, a polyimide laminate was produced from the obtained polyamic acid solution. However, after coating the polyamic acid solution on an alkali-free glass plate, it was dried in a hot air oven at 120°C for 30 minutes. As a result, orange peel-like irregularities were formed on the film surface. Thereafter, in the same manner as in Comparative Example 1, a polyimide laminate having a thickness of 20 μm was obtained.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為11.2重量%且溶液中之溶劑之比率成為NMP/丁基溶纖劑=90/10之方式，添加NMP及丁基溶纖劑進行稀釋，獲得於23℃下顯示黏度為9.0Pa．s且水分為2000ppm之聚醯胺酸溶液。 For the polyamic acid solution obtained in Synthesis Example 1, the NMP and butyl cellosolve were added in such a manner that the solid content concentration became 11.2% by weight and the ratio of the solvent in the solution became NMP/butyl cellosolve = 90/10 Dilute to obtain a viscosity of 9.0Pa at 23℃. s Polyamic acid solution with a moisture content of 2000 ppm.
與實施例1同樣地由所獲得之聚醯胺酸溶液製造聚醯亞胺積層體。然而，將該聚醯胺酸溶液塗佈於無鹼玻璃板後，於熱風烘箱內以 120℃乾燥30分鐘，結果於膜表面形成有橘皮狀之凹凸。其後，與比較例1同樣地，獲得聚醯亞胺層之厚度為20μm之聚醯亞胺積層體。 In the same manner as in Example 1, a polyimide laminate was produced from the obtained polyamic acid solution. However, after applying the polyamic acid solution to the alkali-free glass plate, in a hot air oven After drying at 120°C for 30 minutes, orange peel-like irregularities were formed on the film surface. Thereafter, in the same manner as in Comparative Example 1, a polyimide laminate having a thickness of 20 μm was obtained.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為11.2重量%且溶液中之溶劑之比率成為NMP/γ-丁內酯=90/10之方式，添加NMP及γ-丁內酯進行稀釋，獲得於23℃下顯示黏度為6.8Pa．s且水分為2000ppm之聚醯胺酸溶液。 For the polyamic acid solution obtained in Synthesis Example 1, NMP and γ- were added in such a manner that the solid content concentration became 11.2% by weight and the ratio of the solvent in the solution became NMP/γ-butyrolactone=90/10. Butyrolactone was diluted to obtain a viscosity of 6.8 Pa at 23 °C. s Polyamic acid solution with a moisture content of 2000 ppm.
與實施例1同樣地由所獲得之聚醯胺酸溶液製造聚醯亞胺積層體。然而，將該聚醯胺酸溶液塗佈於無鹼玻璃板後，於熱風烘箱內以120℃乾燥30分鐘，結果於膜表面形成有橘皮狀之凹凸。其後，與比較例1同樣地，獲得聚醯亞胺層之厚度為20μm之聚醯亞胺積層體。 In the same manner as in Example 1, a polyimide laminate was produced from the obtained polyamic acid solution. However, after coating the polyamic acid solution on an alkali-free glass plate, it was dried in a hot air oven at 120°C for 30 minutes. As a result, orange peel-like irregularities were formed on the film surface. Thereafter, in the same manner as in Comparative Example 1, a polyimide laminate having a thickness of 20 μm was obtained.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為12.8重量%且溶液中之溶劑之比率成為NMP/二異丁基酮=90/10之方式，添加NMP及二異丁基酮進行稀釋，獲得於23℃下顯示黏度為8.0Pa．s且水分為2000ppm之聚醯胺酸溶液。 For the polyamic acid solution obtained in Synthesis Example 1, NMP and diiso were added in such a manner that the solid content concentration became 12.8% by weight and the ratio of the solvent in the solution became NMP/diisobutyl ketone=90/10 Butyl ketone was diluted to obtain a viscosity of 8.0 Pa at 23 °C. s Polyamic acid solution with a moisture content of 2000 ppm.
與實施例1同樣地由所獲得之聚醯胺酸溶液製造聚醯亞胺積層體。然而，將該聚醯胺酸溶液塗佈於無鹼玻璃板後，於熱風烘箱內以120℃乾燥30分鐘，結果於膜表面形成有橘皮狀之凹凸。其後，與比較例1同樣地，獲得聚醯亞胺層之厚度為20μm之聚醯亞胺積層體。 In the same manner as in Example 1, a polyimide laminate was produced from the obtained polyamic acid solution. However, after coating the polyamic acid solution on an alkali-free glass plate, it was dried in a hot air oven at 120°C for 30 minutes. As a result, orange peel-like irregularities were formed on the film surface. Thereafter, in the same manner as in Comparative Example 1, a polyimide laminate having a thickness of 20 μm was obtained.
觀察比較例1~6所獲得之積層體，表面狀態較差，未獲得厚度均勻之聚醯亞胺層，因此無法進行物性之測定。再者，關於聚醯亞胺層之表面性之評價，示於表2。 Observing the laminates obtained in Comparative Examples 1 to 6, the surface state was poor, and a polyimide layer with a uniform thickness was not obtained, so physical properties could not be measured. In addition, the evaluation of the surface properties of the polyimide layer is shown in Table 2.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為 13.0重量%之方式添加NMP進行稀釋，獲得於23℃下顯示黏度為7.0Pa．s且水分為2000ppm之聚醯胺酸溶液。 For the polyamic acid solution obtained in Synthesis Example 1, the solid content concentration becomes NMP was added for dilution at 13.0% by weight to obtain a viscosity of 7.0 Pa at 23°C. s Polyamic acid solution with a moisture content of 2000 ppm.
利用棒式塗佈機將所獲得之聚醯胺酸溶液以乾燥後之厚度成為20μm之方式流延於兩邊150mm、厚度0.7mm之正方形之無鹼玻璃板(康寧公司製造之Eagle XG)上，於熱風烘箱內以60℃乾燥20分鐘。其後，將該無鹼玻璃板於氮氣環境下自20℃以4℃/分鐘升溫至150℃，以150℃保持20分鐘，繼而以4℃/分鐘升溫至350℃，以350℃加熱20分鐘，進而繼而以4℃/分鐘升溫至450℃，以450℃保持10分鐘。因此，獲得聚醯亞胺層之厚度為20μm之聚醯亞胺積層體。 Using a bar coater, the obtained polyamic acid solution was cast on a square alkali-free glass plate (Eagle XG manufactured by Corning Corporation) with a thickness of 0.7 mm on both sides and a thickness of 20 μm after drying. Dry in a hot air oven at 60°C for 20 minutes. Thereafter, the alkali-free glass plate was heated from 20°C at 4°C/min to 150°C under a nitrogen atmosphere, held at 150°C for 20 minutes, and then heated to 350°C at 4°C/min, and heated at 350°C for 20 minutes Then, the temperature was further increased to 450°C at 4°C/min and maintained at 450°C for 10 minutes. Therefore, a polyimide laminate having a thickness of 20 μm was obtained.
對於合成例1中所獲得之聚醯胺酸溶液，以固形物成分濃度成為13.0重量%之方式添加NMP進行稀釋，獲得於23℃下顯示黏度為7.0Pa．s且水分為2000ppm之聚醯胺酸溶液。 For the polyamic acid solution obtained in Synthesis Example 1, NMP was added so as to have a solid content concentration of 13.0% by weight to be diluted, and a viscosity of 7.0 Pa at 23°C was obtained. s Polyamic acid solution with a moisture content of 2000 ppm.
利用棒式塗佈機將所獲得之聚醯胺酸溶液以乾燥後之厚度成為20μm之方式流延於兩邊150mm、厚度0.7mm之正方形之無鹼玻璃板(康寧公司製造之Eagle XG)上，於熱風烘箱內以80℃進行乾燥20分鐘。其後，將該無鹼玻璃板於氮氣環境下自20℃以4℃/分鐘升溫至150℃，以150℃保持20分鐘，繼而以4℃/分鐘升溫至350℃，以350℃加熱20分鐘，進而繼而以4℃/分鐘升溫至450℃，以450℃保持10分鐘。藉此，獲得聚醯亞胺層之厚度為20μm之聚醯亞胺積層體。 Using a bar coater, the obtained polyamic acid solution was cast on a square alkali-free glass plate (Eagle XG manufactured by Corning Corporation) with a thickness of 0.7 mm on both sides and a thickness of 20 μm after drying. Dry in a hot air oven at 80°C for 20 minutes. Thereafter, the alkali-free glass plate was heated from 20°C at 4°C/min to 150°C under a nitrogen atmosphere, held at 150°C for 20 minutes, and then heated to 350°C at 4°C/min, and heated at 350°C for 20 minutes Then, the temperature was further increased to 450°C at 4°C/min and maintained at 450°C for 10 minutes. With this, a polyimide laminate having a thickness of 20 μm was obtained.
觀察參考例1及比較例7所獲得之積層體，於聚醯亞胺層與無鹼玻璃之間未觀察到氣泡及隆起，於加熱中無自然剝離之情況。並且，能夠自無鹼玻璃板剝離聚醯亞胺層。 When observing the laminates obtained in Reference Example 1 and Comparative Example 7, no bubbles and swelling were observed between the polyimide layer and the alkali-free glass, and there was no natural peeling during heating. In addition, the polyimide layer can be peeled from the alkali-free glass plate.
換言之，藉由自比較例1中之乾燥起始溫度120℃，使參考例1及 比較例7中之乾燥起始溫度降低至60℃或80℃，而將表面性自D改善至B或C。然而，由於在此種100℃以下之乾燥起始溫度中，加熱時間及冷卻時間變長，故而生產性降低。進而於參考例1及比較例7中，線膨脹係數成為15ppm/K及17ppm/K，與玻璃基板之線膨脹係數之差成為5ppm/K以上。 In other words, the reference example 1 and The drying start temperature in Comparative Example 7 was reduced to 60°C or 80°C, and the surface property was improved from D to B or C. However, at such a drying starting temperature of 100° C. or lower, the heating time and cooling time become longer, so the productivity decreases. Furthermore, in Reference Example 1 and Comparative Example 7, the linear expansion coefficients became 15 ppm/K and 17 ppm/K, and the difference from the linear expansion coefficient of the glass substrate became 5 ppm/K or more.
<聚醯胺酸溶液之製造> <Manufacture of Polyamic Acid Solution>
於具備附聚四氟乙烯製密封栓之攪拌器、攪拌翼、及氮氣導入管之容積2L之玻璃製可分離式燒瓶中，加入NMP 780.0g、PDA 59.2g、ODA 0.9g，將溶液一面於油浴中加熱至50.0℃一面於氮氣環境下攪拌30分鐘。 In a 2L glass separable flask equipped with a stirrer, stirring wing, and nitrogen introduction tube with a sealing plug made of polytetrafluoroethylene, add NMP 780.0g, PDA 59.2g, ODA 0.9g, and place the solution on the side Heat to 50.0°C in an oil bath while stirring under a nitrogen atmosphere for 30 minutes.
確認原料均勻溶解後，加入BPDA 151.8g，一面於氮氣環境下攪拌10分鐘一面將溶液之溫度調整至約90℃直至原料完全溶解。進而一面以固定之溫度進行加熱，一面持續攪拌而降低黏度，獲得於23℃下顯示黏度41泊之黏稠之聚醯胺酸溶液。 After confirming that the raw materials were uniformly dissolved, 151.8 g of BPDA was added, and the temperature of the solution was adjusted to about 90°C until the raw materials were completely dissolved while stirring for 10 minutes under a nitrogen atmosphere. Furthermore, while heating at a fixed temperature, while continuously stirring to reduce the viscosity, a viscous polyamic acid solution showing a viscosity of 41 poise at 23°C was obtained.
再者，該聚醯胺酸溶液中之二胺化合物及四羧酸二酐之添加濃度相對於全部反應液為22重量%，四羧酸二酐之總莫耳數除以二胺之總莫耳數之莫耳比為0.935。測定聚醯胺酸之分子量，結果Mw=20000。 In addition, the addition concentration of the diamine compound and the tetracarboxylic dianhydride in the polyamic acid solution is 22% by weight relative to the total reaction liquid, and the total moles of tetracarboxylic dianhydride divided by the total mole of diamine The molar ratio of ears is 0.935. The molecular weight of polyamide was determined, and the result was Mw=20,000.
<利用烷氧基矽烷化合物之改性> <Modification using alkoxysilane compounds>
將該反應溶液於水浴中迅速冷卻，將溶液之溫度調整至約50℃。其次，添加γ-APS之1%NMP溶液11.0g、攪拌2小時。 The reaction solution was quickly cooled in a water bath, and the temperature of the solution was adjusted to about 50°C. Next, 11.0 g of a 1% NMP solution of γ-APS was added and stirred for 2 hours.
對於合成例4中所獲得之聚醯胺酸溶液，以固形物成分濃度成為20.5重量%且溶液中之溶劑之比率成為NMP/MIBK=95/5之方式，添加NMP及MIBK進行稀釋，獲得於23℃下顯示黏度為2.5Pa．s且水分 為1500ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1同樣之方式獲得聚醯亞胺積層體。 For the polyamic acid solution obtained in Synthesis Example 4, the NMP and MIBK were added and diluted in such a manner that the solid content concentration became 20.5% by weight and the ratio of the solvent in the solution became NMP/MIBK=95/5. The viscosity at 23℃ is 2.5Pa. s and moisture It is a solution of 1500 ppm of polyamic acid. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
對於合成例4中所獲得之聚醯胺酸溶液，以固形物成分濃度成為20.5重量%且溶液中之溶劑之比率成為NMP/THF=95/5之方式，添加NMP及THF進行稀釋，獲得於23℃下顯示黏度為2.4Pa．s，水分為1500ppm之聚醯胺酸溶液。並且，使用所獲得之聚醯胺酸溶液，以與實施例1相同之方式獲得聚醯亞胺積層體。 The polyamic acid solution obtained in Synthesis Example 4 was diluted by adding NMP and THF in such a manner that the solid content concentration became 20.5% by weight and the ratio of the solvent in the solution became NMP/THF=95/5. The viscosity at 23℃ is 2.4Pa. s, Polyamic acid solution with a water content of 1500 ppm. Furthermore, using the obtained polyamic acid solution, a polyimide laminate was obtained in the same manner as in Example 1.
觀察實施例11及12所獲得之積層體，表面性良好，但由於厚度均勻之聚醯亞胺層較脆而無法進行剝離，故而無法進行物性之測定。再者，關於聚醯亞胺層之表面性之評價，示於表2。 The laminates obtained in Examples 11 and 12 were observed to have good surface properties. However, the polyimide layer with a uniform thickness was brittle and could not be peeled off, so physical properties could not be measured. In addition, the evaluation of the surface properties of the polyimide layer is shown in Table 2.
實施例1~12之聚醯亞胺積層體中之聚醯亞胺層即便厚度為20μm左右，表面亦較平滑。又，於聚醯亞胺積層體中，於聚醯亞胺層與無鹼玻璃板之間未產生氣泡。與此相對，比較例1~7之聚醯亞胺積層體中之聚醯亞胺層之表面平滑性較差，不適合顯示器基板用途。 The polyimide layer in the polyimide laminates of Examples 1 to 12 has a smooth surface even if the thickness is about 20 μm. In addition, in the polyimide laminate, no bubbles were generated between the polyimide layer and the alkali-free glass plate. In contrast, the polyimide layer in the polyimide laminates of Comparative Examples 1 to 7 has poor surface smoothness, and is not suitable for display substrate applications.
又，實施例1~12之聚醯亞胺層自無鹼玻璃板剝離之後，亦無捲曲及翹曲。其原因在於，聚醯亞胺層之線膨脹係數為20ppm/K以下，與聚醯亞胺層正下方之基板之線膨脹係數接近(基板與聚醯亞胺層之線膨脹係數之差為10ppm/K以下)。 In addition, after the polyimide layers of Examples 1 to 12 were peeled from the alkali-free glass plate, there was no curl or warpage. The reason is that the linear expansion coefficient of the polyimide layer is 20 ppm/K or less, which is close to the linear expansion coefficient of the substrate directly under the polyimide layer (the difference between the linear expansion coefficients of the substrate and the polyimide layer is 10 ppm) /K below).
再者，實施例1~12、比較例1~7及參考例1之全部中之聚醯胺酸溶液之水分為500ppm以上且3000ppm以下，儲存時之黏度變化不影響該等之結果。 Furthermore, the moisture of the polyamic acid solution in all of Examples 1 to 12, Comparative Examples 1 to 7 and Reference Example 1 is 500 ppm or more and 3000 ppm or less, and the change in viscosity during storage does not affect these results.
本發明可較佳地利用於例如平板顯示器及電子紙等電子裝置之領域。 The present invention can be preferably used in the field of electronic devices such as flat panel displays and electronic paper.
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