JP2019143144A - Composition for forming releasing layer - Google Patents
Composition for forming releasing layer Download PDFInfo
- Publication number
- JP2019143144A JP2019143144A JP2019040405A JP2019040405A JP2019143144A JP 2019143144 A JP2019143144 A JP 2019143144A JP 2019040405 A JP2019040405 A JP 2019040405A JP 2019040405 A JP2019040405 A JP 2019040405A JP 2019143144 A JP2019143144 A JP 2019143144A
- Authority
- JP
- Japan
- Prior art keywords
- release layer
- substrate
- composition
- formula
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 97
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 28
- 239000011521 glass Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 125000000962 organic group Chemical group 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 134
- 230000015572 biosynthetic process Effects 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 13
- 239000011254 layer-forming composition Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000004305 biphenyl Chemical group 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 27
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 24
- 229920003270 Cymel® Polymers 0.000 description 23
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 18
- 239000002585 base Substances 0.000 description 17
- 239000010409 thin film Substances 0.000 description 17
- 239000004642 Polyimide Substances 0.000 description 15
- 229920001721 polyimide Polymers 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
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- 230000000052 comparative effect Effects 0.000 description 12
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- 150000001875 compounds Chemical class 0.000 description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 10
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- -1 and more preferably Chemical group 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical class NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000007974 melamines Chemical class 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 3
- 238000006358 imidation reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920003319 Araldite® Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 0 OC(c(cc1)c2cc1C(O*OC(c(cc1C(O3)=O)ccc1C3=O)=O)=O)OC2=O Chemical compound OC(c(cc1)c2cc1C(O*OC(c(cc1C(O3)=O)ccc1C3=O)=O)=O)OC2=O 0.000 description 2
- 239000004793 Polystyrene Substances 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 class N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 125000004849 alkoxymethyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229920002457 flexible plastic Polymers 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical class C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- KATAXDCYPGGJNJ-UHFFFAOYSA-N 1,3-bis(oxiran-2-ylmethoxy)propan-2-ol Chemical compound C1OC1COCC(O)COCC1CO1 KATAXDCYPGGJNJ-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- QCILMAMLEHOLRX-UHFFFAOYSA-N 2-(3-aminophenyl)-3h-benzimidazol-5-amine Chemical compound NC1=CC=CC(C=2NC3=CC(N)=CC=C3N=2)=C1 QCILMAMLEHOLRX-UHFFFAOYSA-N 0.000 description 1
- IPFOLFNDBVVUNS-UHFFFAOYSA-N 2-(trifluoromethyl)benzene-1,3-diamine Chemical compound NC1=CC=CC(N)=C1C(F)(F)F IPFOLFNDBVVUNS-UHFFFAOYSA-N 0.000 description 1
- ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 2-(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C(F)(F)F)=C1 ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 0.000 description 1
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 1
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 1
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- 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
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- DMOSWVCKHJJLLN-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-2-methylaniline Chemical compound C1=C(N)C(C)=CC(C=2C(=CC(N)=CC=2)C)=C1 DMOSWVCKHJJLLN-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- QQWWWAQUMVHHQN-UHFFFAOYSA-N 4-(4-amino-4-phenylcyclohexa-1,5-dien-1-yl)aniline Chemical group C1=CC(N)=CC=C1C1=CCC(N)(C=2C=CC=CC=2)C=C1 QQWWWAQUMVHHQN-UHFFFAOYSA-N 0.000 description 1
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001046 glycoluril group Chemical class [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000000123 paper 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
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 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
- 150000003222 pyridines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
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Abstract
Description
本発明は、ガラス基板直上に設ける剥離層を形成するための組成物に関する。 The present invention relates to a composition for forming a release layer provided directly on a glass substrate.
近年、電子デバイスには曲げるという機能付与や薄型化および軽量化といった性能が求められている。このことから、従来の重く脆弱で曲げることができないガラス基板に代わって、軽量なフレキシブルプラスチック基板を用いることが求められる。また、新世代ディスプレイでは、軽量なフレキシブルプラスチック基板を用いる、アクティブフルカラー(active full-color)TFTディスプレイパネルの開発が求められている。
そこで、樹脂フィルムを基板とした電子デバイスの製造方法が各種検討され始めており、新世代ディスプレイでは、既存のTFT設備を転用可能なプロセスで製造検討が進められている。
In recent years, electronic devices have been required to have the functions of bending, thinning and lightening. For this reason, it is required to use a lightweight flexible plastic substrate in place of the conventional glass substrate that is fragile and cannot be bent. In the new generation display, development of an active full-color TFT display panel using a lightweight flexible plastic substrate is required.
Therefore, various methods for manufacturing electronic devices using a resin film as a substrate are being studied, and in the new generation display, manufacturing studies are being carried out in a process that can divert existing TFT equipment.
特許文献1、2及び3は、ガラス基板上にアモルファスシリコン薄膜層を形成し、その薄膜層上にプラスチック基板を形成した後に、ガラス面側からレーザーを照射して、アモルファスシリコンの結晶化に伴い発生する水素ガスによりプラスチック基板をガラス基板から剥離する方法を開示する。
また、特許文献4は、特許文献1〜3開示の技術を用いて被剥離層(特許文献4において「被転写層」と記載される)をプラスチックフィルムに貼りつけて液晶表示装置を完成させる方法を開示する。
In Patent Documents 1, 2, and 3, an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side to accompany crystallization of amorphous silicon. A method of peeling a plastic substrate from a glass substrate with generated hydrogen gas is disclosed.
Patent Document 4 discloses a method for attaching a layer to be peeled (described as “transfer target layer” in Patent Document 4) to a plastic film by using the techniques disclosed in Patent Documents 1 to 3 to complete a liquid crystal display device. Is disclosed.
しかし、特許文献1〜4開示の方法、特に特許文献4開示の方法は、透光性の高い基板を使用することが必須であり、基板を通過させ、さらに非晶質シリコンに含まれる水素を放出させるのに十分なエネルギーを与えるため、比較的大きなレーザー光の照射が必要とされ、被剥離層に損傷を与えてしまうという問題がある。また、レーザー処理に長時間を要し、大きな面積を有する被剥離層を剥離するのは困難であるため、デバイス作製の生産性を挙げることは難しい、という問題もある。 However, in the methods disclosed in Patent Documents 1 to 4, particularly the method disclosed in Patent Document 4, it is essential to use a highly light-transmitting substrate, and the hydrogen contained in amorphous silicon is allowed to pass through the substrate. In order to give energy sufficient to emit, there is a problem that irradiation with a relatively large laser beam is required and the layer to be peeled is damaged. In addition, since it takes a long time for laser treatment and it is difficult to peel off a layer to be peeled having a large area, there is a problem that it is difficult to increase the productivity of device fabrication.
そこで、本発明の目的は、上記課題を解決することにある。
具体的には、本発明の目的は、フレキシブル電子デバイスに適用される基板に損傷を与えることなく剥離させるための剥離層を形成するための組成物を提供することにある。
Therefore, an object of the present invention is to solve the above problems.
Specifically, the objective of this invention is providing the composition for forming the peeling layer for making it peel without damaging the board | substrate applied to a flexible electronic device.
また、本発明の目的は、上記目的に加えて、又は上記目的以外に、剥離層が設けられるガラス基板との密着性が維持されガラス基板との界面での剥離が生じない一方、剥離層より上部に形成される層又は層群を剥離層から簡易に剥離することができる、該剥離層を形成するための組成物を提供することにある。 Further, in addition to the above object or other than the above object, the object of the present invention is to maintain adhesion with a glass substrate on which a release layer is provided and does not cause peeling at the interface with the glass substrate. An object of the present invention is to provide a composition for forming a release layer, which can easily peel a layer or a group of layers formed thereon from the release layer.
本発明者は今般、以下のような発明を見出した。すなわち、本発明者は、特定の構造のモノマー単位を50モル%以上含み、重量平均分子量が一定の値以上であるポリアミック酸と、有機溶媒とを含む組成物を用いて剥離層を形成すると、その層は、フレキシブル電子デバイス等に適用される基板に損傷を与えることなく剥離させることができる好適な特性を有していることを、予想外にも見出した。この層は、剥離層が設けられるガラス基板との密着性が維持されガラス基板との界面での剥離が生じ難い一方で、ガラス基板とは反対側の剥離層より上部に形成される層又は層群については、剥離層から簡易に剥離することができるものであった。本発明はかかる知見に基づくものである。 The present inventor has now found the following invention. That is, the present inventor forms a release layer using a composition containing a polyamic acid having a monomer unit having a specific structure of 50 mol% or more and a weight average molecular weight of a certain value or more, and an organic solvent. It has unexpectedly been found that the layer has suitable properties that can be peeled off without damaging the substrate applied to the flexible electronic device or the like. This layer is a layer or layer formed above the release layer on the side opposite to the glass substrate, while maintaining adhesion to the glass substrate on which the release layer is provided and hardly causing peeling at the interface with the glass substrate. About a group, it was able to peel easily from a peeling layer. The present invention is based on such knowledge.
<1> 下記の式(1)で表されるモノマー単位を50モル%以上含み、重量平均分子量が10,000以上であるポリアミック酸と、有機溶媒とを含む、剥離層形成用組成物。
[式中、X1は、4価の有機基を表し、Y1は、下記の式(P)で表される2価の基を表す:
(式中、Rは、F、Cl、炭素数1〜3のアルキル基、又はフェニル基を表し、mは、0〜4の整数を表し、かつ、rは1〜4の整数を表す)]。
<1> A composition for forming a release layer, comprising a polyamic acid containing 50 mol% or more of a monomer unit represented by the following formula (1) and having a weight average molecular weight of 10,000 or more and an organic solvent.
[Wherein, X 1 represents a tetravalent organic group, and Y 1 represents a divalent group represented by the following formula (P):
(In the formula, R represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, m represents an integer of 0 to 4, and r represents an integer of 1 to 4)] .
<2> 前記<1>において、前記Y1が、下記の式(P1)〜(P3)のいずれかで表される2価の基であるのがよい。
(式中、
R1、R2、R3、R4、R5及びR6は、同一であっても異なっていてもよく、F、Cl、炭素数1〜3のアルキル基、又はフェニル基を表し、
m1、m2、m3、m4、m5及びm6は、同一であっても異なっていてもよく、0〜4の整数を表す)。
<2> In the above item <1>, the Y 1 may be a divalent group represented by any of the following formulas (P1) to (P3).
(Where
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group,
m1, m2, m3, m4, m5 and m6 may be the same or different and represent an integer of 0 to 4).
<3> 前記<2>前記Y1が、少なくとも式(P1)で表される2価の基を含むのがよい。
<3> The <2> Y 1 may include at least a divalent group represented by the formula (P1).
<4> 前記<1>〜<3>のいずれかにおいて、ポリアミック酸が、下記の式(2)で表されるモノマー単位をさらに含むのがよい。
[式中、
X1は、前記<1>で定義されたとおりであり、Y2は、下記の式(P4)で表される基を表す:
(式中、
R7、及びR8は、同一であっても異なっていてもよく、F、Cl、炭素数1〜3のアルキル基、又はフェニル基を表し、
R’は、水素原子、炭素数1〜3のアルキル基、又はフェニル基を表し、 lは0〜4の整数を表し、かつ
mは、前記<1>で定義されたとおりである)]。
<4> In any one of the above items <1> to <3>, the polyamic acid may further include a monomer unit represented by the following formula (2).
[Where:
X 1 is as defined in <1> above, and Y 2 represents a group represented by the following formula (P4):
(Where
R 7 and R 8 may be the same or different and each represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group;
R ′ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, l represents an integer of 0 to 4, and m is as defined in the above <1>).
<5> 前記<1>〜<4>のいずれかにおいて、X1が、4価の芳香族基であるのがよい。 <5> In any one of the above items <1> to <4>, X 1 may be a tetravalent aromatic group.
<6> 前記<5>において、前記4価の芳香族基が、ベンゼン骨格、ナフタレン骨格及びビフェニル骨格から選ばれる少なくとも1種を有するものであるのがよい。 <6> In the above item <5>, the tetravalent aromatic group may have at least one selected from a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton.
<7> 前記<1>〜<6>のいずれかにおいて、前記有機溶媒が、下記式(A)又は(B)で表される溶媒であるのがよい。
(式中、Ra及びRbは同一であっても異なっていてもよく、炭素数1〜4のアルキル基を表し、hは自然数を表す)。
<7> In any one of the above items <1> to <6>, the organic solvent may be a solvent represented by the following formula (A) or (B).
(In the formula, R a and R b may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and h represents a natural number).
<8> 前記<1>〜<7>のいずれかにおいて、前記ポリアミック酸中の前記式(1)で表されるモノマー単位の含有量が60モル%以上であるのがよい。 <8> In any one of the above items <1> to <7>, the content of the monomer unit represented by the formula (1) in the polyamic acid may be 60 mol% or more.
<9> 前記<1>〜<8>のいずれかにおいて、本発明による剥離層形成用組成物は、ガラス基板直上に設ける剥離層を形成するためのものであるのがよい。 <9> In any one of the above items <1> to <8>, the composition for forming a release layer according to the present invention may be for forming a release layer provided directly on a glass substrate.
<10> フレキシブル電子デバイスに適用されるフレキシブル基板と、ベース基板との間に形成される剥離層であって、前記<1>〜<9>のいずれかの剥離層形成用組成物を用いて作製される剥離層。 <10> A release layer formed between a flexible substrate applied to a flexible electronic device and a base substrate, using the release layer forming composition according to any one of <1> to <9>. A release layer to be produced.
<11> フレキシブル電子デバイスに適用される基板構造であって、
ベース基板と、
1又は2以上の領域で、前記ベース基体を覆う剥離層であって、前記<1>〜<9>のいずれかの剥離層形成用組成物により形成された剥離層と、
前記ベース基板と、前記剥離層を覆う、フレキシブル基板
とを含み、
前記フレキシブル基板と前記剥離層との密着力が、前記剥離層と前記ベース基体との密着力より大きいことを特徴とする、基板構造。
<11> A substrate structure applied to a flexible electronic device,
A base substrate;
A release layer that covers the base substrate in one or more regions, and is formed of the release layer forming composition according to any one of <1> to <9>;
Including the base substrate and a flexible substrate covering the release layer;
A substrate structure, wherein an adhesion force between the flexible substrate and the release layer is larger than an adhesion force between the release layer and the base substrate.
<12> 前記<11>において、ベース基板が、ガラスを含むのがよい。 <12> In the above item <11>, the base substrate may include glass.
<13> 前記<1>〜<9>のいずれかの剥離層形成用組成物を用いることを特徴とする、剥離層の製造方法。一つの好ましい態様において、前記剥離層の製造方法は、前記剥離層形成用樹脂組成物を基板へ塗布し、加熱する工程を含む。 <13> A method for producing a release layer, comprising using the release layer forming composition according to any one of <1> to <9>. In one preferable aspect, the method for producing the release layer includes a step of applying the release layer forming resin composition to a substrate and heating the substrate.
<14> フレキシブル電子デバイスに適用される基板構造の作製方法であって、
ベース基板を準備する工程、
1又は2以上の領域で、前記ベース基体を覆う剥離層を、前記<1>〜<9>のいずれかの剥離層形成用組成物を用いて作製する工程、
前記ベース基板と、前記剥離層上に、フレキシブル基板を形成する工程
を含み、
前記フレキシブル基板と前記剥離層との密着力が、前記剥離層と前記ベース基体との密着力より大きいことを特徴とする、作製方法。
<14> A method for producing a substrate structure applied to a flexible electronic device,
Preparing a base substrate,
Producing a release layer covering the base substrate in one or more regions using the release layer forming composition according to any one of <1> to <9>;
Forming a flexible substrate on the base substrate and the release layer;
The manufacturing method characterized by the adhesive force of the said flexible substrate and the said peeling layer being larger than the adhesive force of the said peeling layer and the said base base | substrate.
本発明により、上記課題を解決することができる。
具体的には、本発明により、フレキシブル電子デバイスに適用される基板に損傷を与えることなく剥離させるための剥離層を形成するための組成物を提供することができる。
また、本発明により、上記効果に加えて、又は上記効果以外に、剥離層が設けられるガラス基板との密着性が維持されガラス基板との界面での剥離が生じない一方、剥離層より上部に形成される層又は層群を剥離層から簡易に剥離することができる、該剥離層を形成するための組成物を提供することにある。
The present invention can solve the above problems.
Specifically, according to the present invention, it is possible to provide a composition for forming a release layer for peeling without damaging a substrate applied to a flexible electronic device.
Further, according to the present invention, in addition to the above effects or in addition to the above effects, the adhesion with the glass substrate on which the release layer is provided is maintained, and peeling at the interface with the glass substrate does not occur. It is providing the composition for forming this peeling layer which can peel the layer or layer group formed easily from a peeling layer.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
剥離層形成用組成物
本発明の剥離層形成用組成物は、前記したように、式(1)で表されるモノマー単位を50モル%以上含むポリアミック酸であって、その重量平均分子量が10,000以上であるポリアミック酸と、有機溶媒とを含むものである。
Release Layer Forming Composition As described above, the release layer forming composition of the present invention is a polyamic acid containing 50 mol% or more of the monomer unit represented by the formula (1), and its weight average molecular weight is 10 , 1,000 or more polyamic acid and an organic solvent.
また前記したように、式(1)において、X1は、4価の有機基を表し、Y1は、下記の式(P)で表される2価の基を表す。 Further, as described above, in the formula (1), X 1 represents a tetravalent organic group, and Y 1 represents a divalent group represented by the following formula (P).
また式(P)において、Rは、F、Cl、または炭素数1〜3のアルキル基、又はフェニル基を表し、好ましくは、F、Clを表す。同様に前記の式(P)において、mは、0〜4の整数を表し、好ましくは0〜2を表し、より好ましくは0〜1を表し、特に好ましくは0を表す。また前記の式(P)において、rは1〜3の整数を表す。
なお、炭素数1〜3のアルキル基には、メチル、エチル、n−プロピル、およびi−プロピルが包含され、好ましくは、炭素数1〜3のアルキル基は、メチルであり、より好ましくは、メチルである。
In Formula (P), R represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and preferably represents F or Cl. Similarly, in said Formula (P), m represents the integer of 0-4, Preferably it represents 0-2, More preferably, it represents 0-1, Most preferably, it represents 0. Moreover, in said Formula (P), r represents the integer of 1-3.
The alkyl group having 1 to 3 carbon atoms includes methyl, ethyl, n-propyl, and i-propyl. Preferably, the alkyl group having 1 to 3 carbon atoms is methyl, and more preferably, Methyl.
本発明で用いる式(1)で表されるモノマー単位を有するポリアミック酸の重量平均分子量は、10,000以上である必要があり、好ましくは15,000以上、より好ましくは20,000以上、より一層好ましくは30,000以上である。一方、本発明で用いるポリアミック酸の重量平均分子量の上限値は、通常2,000,000以下であるが、樹脂組成物の粘度が過度に高くなることを抑制することや柔軟性の高い樹脂薄膜を再現性よく得ること等を考慮すると、好ましくは1,000,000以下、より好ましくは200,000以下である。 The weight average molecular weight of the polyamic acid having the monomer unit represented by the formula (1) used in the present invention needs to be 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, more More preferably, it is 30,000 or more. On the other hand, the upper limit value of the weight average molecular weight of the polyamic acid used in the present invention is usually 2,000,000 or less, but it is possible to suppress the viscosity of the resin composition from becoming excessively high or to have a highly flexible resin thin film. In view of obtaining a good reproducibility, etc., it is preferably 1,000,000 or less, more preferably 200,000 or less.
本発明で用いるポリアミック酸は、式(1)で表されるモノマー単位を、50モル%以上、好ましくは60モル%以上、より好ましくは70モル%以上、より一層好ましくは80モル%以上、さらに好ましくは90モル%以上、含有する。このようなモノマー単位の含有量であるポリアミック酸を用いることで、剥離膜に適した特性を持つ樹脂薄膜を再現性よく得ることができる。 In the polyamic acid used in the present invention, the monomer unit represented by the formula (1) is 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, Preferably it contains 90 mol% or more. By using a polyamic acid having such a monomer unit content, a resin thin film having characteristics suitable for a release film can be obtained with good reproducibility.
本発明の好ましい態様によれば、本発明の剥離層形成用組成物が含むポリアミック酸は、式(1)で表されるモノマー単位のみからなるポリマー、すなわち、式(1)で表されるモノマー単位が100モル%で含有されるポリマーである。このとき、このようなポリアミック酸におけるモノマー単位は、それが式(1)で表される限り、特定の1種のみであってもよく、2種以上であってもよい。後者の場合、ポリアミック酸が含む式(1)のモノマー単位の数は、好ましくは2〜4であり、より好ましくは2〜3である。 According to a preferred embodiment of the present invention, the polyamic acid contained in the composition for forming a release layer of the present invention is a polymer composed only of the monomer unit represented by the formula (1), that is, the monomer represented by the formula (1). It is a polymer containing 100 mol% of units. At this time, the monomer unit in such a polyamic acid may be only one specific type or two or more types as long as it is represented by the formula (1). In the latter case, the number of monomer units of the formula (1) contained in the polyamic acid is preferably 2 to 4, more preferably 2 to 3.
本発明においては、式(P)で表される基は、好ましくは式(P1)〜(P3)のいずれかで表される2価の基を含み、より好ましくは式(P1)または(P3)で表される2価の基を含み、より一層好ましくは式(P3)で表される2価の基を含む。 In the present invention, the group represented by the formula (P) preferably includes a divalent group represented by any one of the formulas (P1) to (P3), more preferably the formula (P1) or (P3 ), And more preferably a divalent group represented by the formula (P3).
前記した式(P1)、式(P2)および式(P3)において、R1、R2、R3、R4、R5及びR6は、同一であっても異なっていてもよく、F、Cl、炭素数1〜3のアルキル基、又はフェニル基を表し、好ましくは、F、又はClを表す。
同様にこれら式において、m1、m2、m3、m4、m5及びm6は、同一であっても異なっていてもよく、0〜4の整数を表し、好ましくは0〜2を表し、より好ましくは0〜1を表し、特に好ましくは0を表す。
In the above formula (P1), formula (P2) and formula (P3), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different, and F, Cl represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and preferably represents F or Cl.
Similarly, in these formulas, m1, m2, m3, m4, m5 and m6 may be the same or different and each represents an integer of 0 to 4, preferably 0 to 2, more preferably 0. Represents -1, particularly preferably 0.
本発明で用いるポリアミック酸は、式(1)で表されるモノマー単位以外にも、他のモノマー単位を含んでもよい。このような他のモノマー単位の含有量は、50モル%未満である必要があり、40モル%未満であることが好ましく、30モル%未満であることがより好ましく、20モル%未満であることがより一層好ましく、10モル%未満であることがさらに好ましい。 The polyamic acid used in the present invention may contain other monomer units in addition to the monomer unit represented by the formula (1). The content of such other monomer units needs to be less than 50 mol%, preferably less than 40 mol%, more preferably less than 30 mol%, and less than 20 mol%. Is more preferable, and it is further more preferable that it is less than 10 mol%.
このような他のモノマー単位としては、例えば式(2)のモノマー単位が挙げられる。 Examples of such other monomer units include monomer units of the formula (2).
式(2)において、X1は、4価の有機基を表し、Y2は、前記した式(P4)で表される基を表す。 In the formula (2), X 1 represents a tetravalent organic group, and Y 2 represents a group represented by the above-described formula (P4).
式(P4)において、R7、及びR8は、同一であっても異なっていてもよく、F、Cl、炭素数1〜3のアルキル基、又はフェニル基を表す。R7は、好ましくはF、又はClを表す。R8は、好ましくは、F、又はClを表す。
R’は、水素原子、炭素数1〜3のアルキル基、又はフェニル基を表し、好ましくは、水素原子、又は炭素数1〜3のアルキル基を表し、より好ましくは、水素原子を表す。
さらに、l及びmは、同一であっても異なっていてもよく、0〜4の整数を表し、好ましくは0〜2を表し、より好ましくは0〜1を表し、特に好ましくは0を表す。
In the formula (P4), R 7 and R 8 may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. R 7 preferably represents F or Cl. R 8 preferably represents F or Cl.
R ′ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
Further, l and m may be the same or different and each represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0.
このような他のモノマー単位としては、前記した式(2)のモノマー単位以外にも、o−フェニレンジアミン、m−フェニレンジアミン、p−フェニレンジアミン、2−メチル−1,4−フェニレンジアミン、5−メチル−1,3−フェニレンジアミン、4−メチル−1,3−フェニレンジアミン、2−(トリフルオロメチル)−1,4−フェニレンジアミン、2−(トリフルオロメチル)−1,3−フェニレンジアミン及び4−(トリフルオロメチル)−1,3−フェニレンジアミン、ベンジジン、2,2’−ジメチルベンジジン、3,3’−ジメチルベンジジン、2,3’−ジメチルベンジジン、2,2’−ビス(トリフルオロメチル)ベンジジン、3,3’−ビス(トリフルオロメチル)ベンジジン、2,3’−ビス(トリフルオロメチル)ベンジジン、4,4’−ジフェニルエーテル、4,4’−ビス(4−アミノフェノキシ)ビフェニル、4,4’−ジアミノベンズアニリド、5−アミノ−2−(3−アミノフェニル)−1H−ベンゾイミダゾール、9,9−ビス(4−アミノフェニル)フルオレンといったジアミンと、ピロメリット酸無水物(PMDA)、2,3,6,7−ナフタレンテトラカルボン酸二無水物、4,4’−オキシジフタル酸無水物、3,3’、4,4’−ベンゾフェノンテトラカルボン酸無水物といった酸二無水物とから誘導される構造などが挙げられる。 Examples of such other monomer units include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 5 other than the monomer unit of the above formula (2). -Methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2- (trifluoromethyl) -1,4-phenylenediamine, 2- (trifluoromethyl) -1,3-phenylenediamine And 4- (trifluoromethyl) -1,3-phenylenediamine, benzidine, 2,2′-dimethylbenzidine, 3,3′-dimethylbenzidine, 2,3′-dimethylbenzidine, 2,2′-bis (tri Fluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, 2,3′-bis (trifluorome L) benzidine, 4,4′-diphenyl ether, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminobenzanilide, 5-amino-2- (3-aminophenyl) -1H-benzo Diamines such as imidazole and 9,9-bis (4-aminophenyl) fluorene, pyromellitic anhydride (PMDA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4′-oxydiphthalic acid Examples thereof include structures derived from anhydrides and acid dianhydrides such as 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride.
式(1)及び式(2)において、前記したように、X1は、4価の有機基であるが、好ましくは、4価の芳香族基である。 In Formula (1) and Formula (2), as described above, X 1 is a tetravalent organic group, preferably a tetravalent aromatic group.
X1がとりうる4価の芳香族基は、本発明で用いるポリアミック酸を作成する際に、以下のような芳香族テトラカルボン酸二無水物を使用することで作成が可能である。
すなわち、ピロメリット酸二無水物、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、2,3,3’,4’−ビフェニルテトラカルボン酸二無水物、3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物、1,4,5,8−ナフタレンテトラカルボン酸二無水物、1,2,5,6−ナフタレンテトラカルボン酸二無水物、4,4’−オキシジフタル酸無水物、3,3’,4,4’−ジメチルジフェニルシランテトラカルボン酸二無水物、3,3’,4,4’−テトラフェニルシランテトラカルボン酸二無水物、1,2,3,4−フランテトラカルボン酸二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルプロパン二無水物、4,4’−ヘキサフルオロイソプロピリデンジフタル酸無水物、パラフェニレンジフタル酸二無水物、2,2−ビス―((3,4−ジカルボキシフェニル)−ヘキサフルオロプロパン二無水物、9,9−ビス(3,4−ジカルボキシフェニル)フルオレン二無水物、9,9‘−ビス[4−(3,4−ジカルボキシフェノキシ)フェニル]フルオレン二無水物、3,3′,4,4′−ビフェニルエーテルテトラカルボン酸二無水物、2,3,5,6−ピリジンテトラカルボン酸二無水物、3,4,9,10−ペリレンテトラカルボン酸二無水物、4,4′−スルホニルジフタル酸二無水物、パラテルフェニル−3,4,3’,4’−テトラカルボン酸二無水物、メタテルフェニル−3,3’,4,4’−テトラカルボン酸二無水物、3,3′,4,4′−ジフェニルエーテルテトラカルボン酸二無水物、1,3−ビス(3,4−ジカルボキシフェニル)−1,1,3,3−テトラメチルジシロキサン二無水物、1−(2,3−ジカルボキシフェニル)−3−(3,4−ジカルボキシフェニル)−1,1,3,3−テトラメチルジシロキサン二無水物、3,3’,4,4’−ハイドロキノンジベンゾエートテトラカルボン酸二無水物、2,2’−ビス(4−ヒドロキシフェニル)プロパンジベンゾエート−3,3’,4,4’−テトラカルボン酸等が挙げられる。
Tetravalent aromatic group X 1 can be taken, when creating a polyamic acid used in the present invention, it is possible to create by using an aromatic tetracarboxylic dianhydride as follows.
That is, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4 , 4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride , 4,4'-hexaf Oroisopropylidene diphthalic anhydride, paraphenylene diphthalic dianhydride, 2,2-bis-((3,4-dicarboxyphenyl) -hexafluoropropane dianhydride, 9,9-bis (3 4-dicarboxyphenyl) fluorene dianhydride, 9,9'-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic Acid dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, Paraterphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, metaterphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Diphenyl ether Ditetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 1- (2,3-dicarboxyphenyl) -3- (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 3,3 ', 4,4'-hydroquinone dibenzoate tetracarboxylic dianhydride, 2 2,2′-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic acid and the like.
好ましくは、ここで望ましい芳香族テトラカルボン酸二無水物は、下記の化合物群から選択されるものである。
(式中、R3は、芳香環を少なくとも1つ有する2価の有機基であり、好ましくは、フェニル、ビフェニル、ナフタレン骨格を有する基である)。
Preferably, the aromatic tetracarboxylic dianhydride desired here is selected from the following group of compounds.
(Wherein R 3 is a divalent organic group having at least one aromatic ring, and preferably a group having a phenyl, biphenyl, or naphthalene skeleton).
よって、本発明の好ましい態様によれば、X1がとりうる4価の芳香族基は、ベンゼン骨格、ナフタレン骨格、ビフェニル骨格、ターフェニル骨格のいずれかを有するものであり、より好ましくは、ベンゼン骨格、ナフタレン骨格、ビフェニル骨格のいずれかを有するものであり、さらに好ましくは、ベンゼン骨格、ビフェニル骨格のいずれかを有するものである。 Therefore, according to a preferred embodiment of the present invention, the tetravalent aromatic group that X 1 can take has any of a benzene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a terphenyl skeleton, and more preferably benzene Those having any of a skeleton, a naphthalene skeleton, and a biphenyl skeleton, and more preferably those having any of a benzene skeleton and a biphenyl skeleton.
本発明の好ましい態様によれば、本発明で用いるポリアミック酸は、酸二無水物としての3,3’、4,4’−ビフェニルテトラカルボン酸二無水物(BPDA)(式(4))と、ジアミンとしての、p−フェニレンジアミン(pPDA)(式(5))及び4,4”−ジアミノ−p−ターフェニル(DATP)(式(6))、または酸二無水物としてのピロメリット酸二無水物(PMDA)(式(7))と、ジアミンとしてのpPDA(式(5))とを反応させることで得ることができる。 According to a preferred embodiment of the present invention, the polyamic acid used in the present invention is a 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) (formula (4)) as an acid dianhydride. P-phenylenediamine (pPDA) (formula (5)) and 4,4 ″ -diamino-p-terphenyl (DATP) (formula (6)) as diamine, or pyromellitic acid as acid dianhydride It can be obtained by reacting dianhydride (PMDA) (formula (7)) and pPDA (formula (5)) as a diamine.
上記反応において、3,3’、4,4’−ビフェニルテトラカルボン酸二無水物(BPDA)と、p−フェニレンジアミン(pPDA)及び4,4”−ジアミノ−p−ターフェニル(DATP)からなるジアミン、またはピロメリット酸二無水物(PMDA)と、pPDAの仕込み比(モル比)は、所望するポリアミック酸の分子量やモノマー単位の割合等を勘案して適宜設定することができるが、アミン成分1に対して、通常、酸無水物成分が0.7〜1.3程度とすることができ、好ましく0.8〜1.2程度である。 In the above reaction, it consists of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), p-phenylenediamine (pPDA) and 4,4 ″ -diamino-p-terphenyl (DATP). The charge ratio (molar ratio) of diamine or pyromellitic dianhydride (PMDA) and pPDA can be appropriately set in consideration of the molecular weight of the desired polyamic acid, the proportion of monomer units, and the like. 1, the acid anhydride component can usually be about 0.7 to 1.3, preferably about 0.8 to 1.2.
一方、ジアミンであるpPDAとDATPの仕込み比は、DATPの物質量(m2)を1とした場合に、pPDAの物質量(m1)を、通常1.7〜20程度とすることができるが、好ましくは2.1〜20、より好ましくは2.2〜20、より一層好ましくは2.3〜19、さらに好ましくは2.3〜18である。すなわち、m1とm2は、通常、m1/m2=1.7〜20であり、好ましくは2.1〜20であり、より好ましくは2.2〜20であり、より一層好ましくは2.3〜19であり、さらに好ましくは2.3〜18である。 On the other hand, the charge ratio of pPDA and DATP, which are diamines, is such that the substance amount (m 1 ) of pPDA is usually about 1.7 to 20 when the substance amount (m 2 ) of DATP is 1. However, Preferably it is 2.1-20, More preferably, it is 2.2-20, More preferably, it is 2.3-19, More preferably, it is 2.3-18. That is, m 1 and m 2 are usually m 1 / m 2 = 1.7 to 20, preferably 2.1 to 20, more preferably 2.2 to 20, and even more preferably. It is 2.3-19, More preferably, it is 2.3-18.
上記した反応は有機溶媒中で行う。すなわち、本発明による剥離層形成用組成物は、かかる有機溶媒を含む。ここで使用可能な有機溶媒は、前記反応に悪影響を及ぼさないものであれば、各種溶剤を用いることができる。
具体例としては、m−クレゾール、2−ピロリドン、N−メチル−2−ピロリドン、N−エチル−2−ピロリドン、N−ビニル−2−ピロリドン、N,N−ジメチルアセトアミド、N,N−ジメチルホルムアミド、3−メトキシ−N,N−ジメチルプロピルアミド、3−エトキシ−N,N−ジメチルプロピルアミド、3−プロポキシ−N,N−ジメチルプロピルアミド、3−イソプロポキシ−N,N−ジメチルプロピルアミド、3−ブトキシ−N,N−ジメチルプロピルアミド、3−sec−ブトキシ−N,N−ジメチルプロピルアミド、3−tert−ブトキシ−N,N−ジメチルプロピルアミド、γ−ブチロラクトン等のプロトン性溶剤等が挙げられる。これらは単独で又は2種以上を組み合わせて使用してもよい。
The above reaction is carried out in an organic solvent. That is, the composition for forming a release layer according to the present invention contains such an organic solvent. Any organic solvent can be used as long as it does not adversely affect the reaction.
Specific examples include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide. 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, Protic solvents such as 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3-tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone, etc. Can be mentioned. You may use these individually or in combination of 2 or more types.
本発明の好ましい態様によれば、有機溶媒は、式(A)又は(B)で表される溶媒である。 According to a preferred embodiment of the present invention, the organic solvent is a solvent represented by the formula (A) or (B).
式(A)及び式(B)において、Ra及びRbは同一であっても異なっていてもよく、炭素数1〜4のアルキル基を表し、好ましくは、炭素数1〜3である。またここで、hは、自然数を表し、好ましくは、1〜3である。 In formula (A) and formula (B), R a and R b may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms. Here, h represents a natural number, preferably 1 to 3.
反応温度は、用いる溶媒の融点から沸点までの範囲で適宜設定すればよく、通常0〜100℃程度であるが、得られるポリアミック酸のイミド化を防いでポリアミック酸単位の高含有量を維持するためには、好ましくは0〜70℃程度であり、より好ましくは0〜60℃程度であり、より一層好ましくは0〜50℃程度である。
反応時間は、反応温度や原料物質の反応性に依存するため一概に規定できないが、通常1〜100時間程度である。
What is necessary is just to set reaction temperature suitably in the range from melting | fusing point to boiling point of the solvent to be used, and it is about 0-100 degreeC normally, However, Imidation of the polyamic acid obtained is prevented and high content of a polyamic acid unit is maintained. Therefore, it is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.
Although the reaction time depends on the reaction temperature and the reactivity of the raw material, it cannot be defined unconditionally, but is usually about 1 to 100 hours.
以上説明した方法によって、目的とするポリアミック酸を含む反応溶液を得ることができる。 The reaction solution containing the target polyamic acid can be obtained by the method described above.
本発明においては、通常、上記反応溶液をろ過した後、そのろ液をそのまま、又は、希釈若しくは濃縮し、剥離層形成用組成物として用いる。このようにすることで、得られる樹脂薄膜の耐熱性、柔軟性あるいは線膨張係数特性の悪化の原因となり得る不純物の混入を低減できるだけでなく、効率よく組成物を得ることができる。
希釈や濃縮に用いる溶媒は、特に限定されるものではなく、例えば、上記反応の反応溶媒の具体例と同様のものが挙げられ、それらは単独で又は2種以上を組み合わせて使用してもよい。
In the present invention, usually, after filtering the reaction solution, the filtrate is used as it is, or diluted or concentrated, and used as a release layer forming composition. By doing in this way, not only the contamination of the impurity which can cause the deterioration of the heat resistance of the resin thin film obtained, flexibility, or a linear expansion coefficient characteristic can be reduced, but a composition can be obtained efficiently.
The solvent used for dilution and concentration is not particularly limited, and examples thereof include those similar to the specific examples of the reaction solvent in the above reaction, and these may be used alone or in combination of two or more. .
これらの中でも、平坦性の高い樹脂薄膜を再現性よく得ることを考慮すると、用いる溶剤としては、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチル−2−ピロリドン、1,3−ジメチル−2−イミダゾリジノン、N−エチル−2−ピロリドン、γ−ブチロラクトンが好ましい。 Among these, considering that a highly flat resin thin film can be obtained with good reproducibility, the solvent used is N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3. -Dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone and γ-butyrolactone are preferred.
ポリアミック酸の剥離層形成用組成物総質量に対する濃度は、作製する薄膜(剥離層)の厚みや組成物粘度等を勘案して適宜設定するものではあるが、通常0.5〜30質量%程度、好ましくは5〜25質量%程度である。 The concentration of the polyamic acid with respect to the total mass of the release layer forming composition is appropriately set in consideration of the thickness of the thin film to be produced (release layer), the composition viscosity, and the like, but is usually about 0.5 to 30% by mass. The amount is preferably about 5 to 25% by mass.
また、剥離層形成用組成物の粘度も、作製する薄膜の厚み等勘案し適宜設定するものではあるが、特に0.05〜5μm程度の厚さの樹脂薄膜を再現性よく得ること目的とする場合、通常、25℃で10〜10,000mPa・s程度、好ましくは20〜1000mPa・s程度、より好ましくは、20〜200mPa・s程度である。
ここで、剥離層形成用組成物の粘度は、市販の液体の粘度測定用粘度計を使用して、例えば、JIS K7117−2に記載の手順を参照して、剥離層形成用組成物の温度25℃の条件にて測定することができる。好ましくは、粘度計としては、円錐平板型(コーンプレート型)回転粘度計を使用し、好ましくは同型の粘度計で標準コーンロータとして1°34‘×R24を使用して、剥離層形成用組成物の温度25℃の条件にて測定することができる。このような回転粘度計としては、例えば、東機産業株式会社製TVE−25Hが挙げられる。
Further, the viscosity of the composition for forming a release layer is also set as appropriate in consideration of the thickness of the thin film to be produced. In particular, the object is to obtain a resin thin film having a thickness of about 0.05 to 5 μm with good reproducibility. In this case, it is usually about 10 to 10,000 mPa · s at 25 ° C., preferably about 20 to 1000 mPa · s, and more preferably about 20 to 200 mPa · s.
Here, the viscosity of the composition for forming a release layer is measured using a commercially available liquid viscosity measurement viscometer, for example, referring to the procedure described in JIS K7117-2, and the temperature of the composition for forming a release layer. It can be measured at 25 ° C. Preferably, a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably 1 ° 34 ′ × R24 is used as a standard cone rotor with the same type viscometer. It can be measured under the condition that the temperature of the product is 25 ° C. An example of such a rotational viscometer is TVE-25H manufactured by Toki Sangyo Co., Ltd.
なお、本発明の組成物は、ポリアミック酸と有機溶媒の他に、種々の成分を有してもよい。例えば、架橋剤(以下、架橋性化合物ともいう。)を挙げることができるがこれらに限定されない。 In addition, the composition of this invention may have a various component other than a polyamic acid and an organic solvent. Examples thereof include, but are not limited to, a crosslinking agent (hereinafter also referred to as a crosslinkable compound).
前記架橋性化合物としては、例えばエポキシ基を2個以上含有する化合物、アミノ基の水素原子がメチロール基、アルコキシメチル基又はその両方で置換された基を有する、メラミン誘導体、ベンゾグアナミン誘導体又はグリコールウリルなどが挙げられるが、これらに限定されない。 Examples of the crosslinkable compound include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative or glycoluril having a hydrogen atom of an amino group substituted with a methylol group, an alkoxymethyl group or both. However, it is not limited to these.
以下に、架橋性化合物の具体例を挙げるが、これに限定されない。
エポキシ基を2個以上含有する化合物としては、エポリードGT−401、エポリードGT−403、エポリードGT−301、エポリードGT−302、セロキサイド2021、セロキサイド3000(以上、株式会社ダイセル製)等のシクロヘキセン構造を有するエポキシ化合物;エピコート1001、エピコート1002、エピコート1003、エピコート1004、エピコート1007、エピコート1009、エピコート1010、エピコート828(以上、ジャパンエポキシレジン株式会社製(現:三菱化学株式会社製、jER(登録商標)シリーズ))等のビスフェノールA型エポキシ化合物;エピコート807(ジャパンエポキシレジン株式会社製)等のビスフェノールF型エポキシ化合物;エピコート152、エピコート154(以上、ジャパンエポキシレジン株式会社製(現:三菱化学株式会社製、jER(登録商標)シリーズ))、EPPN201、EPPN202(以上、日本化薬株式会社製)等のフェノールノボラック型エポキシ化合物;ECON−102、ECON−103S、ECON−104S、ECON−1020、ECON−1025、ECON−1027(以上、日本化薬株式会社製)、エピコート180S75(ジャパンエポキシレジン株式会社(現:三菱化学株式会社製、jER(登録商標)シリーズ)製)等のクレゾールノボラック型エポキシ化合物;V8000−C7(DIC株式会社製)等のナフタレン型エポキシ化合物;デナコールEX−252(ナガセケムテックス株式会社製)、CY175、CY177、CY179、アラルダイトCY−182、アラルダイトCY−192、アラルダイトCY−184(以上、BASF社製)、エピクロン200、エピクロン400(以上、DIC株式会社製)、エピコート871、エピコート872(以上、ジャパンエポキシレジン株式会社製(現:三菱化学株式会社製、jER(登録商標)シリーズ))、ED−5661、ED−5662(以上、セラニーズコーティング株式会社製)等の脂環式エポキシ化合物;デナコールEX−611、デナコールEX−612、デナコールEX−614、デナコールEX−622、デナコールEX−411、デナコールEX−512、デナコールEX−522、デナコールEX−421、デナコールEX−313、デナコールEX−314、デナコールEX−312(以上、ナガセケムテックス株式会社製)等の脂肪族ポリグリシジルエーテル化合物が挙げられる。
Although the specific example of a crosslinkable compound is given to the following, it is not limited to this.
Examples of the compound containing two or more epoxy groups include cyclohexene structures such as Epolide GT-401, Epolide GT-403, Epolide GT-301, Epolide GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Corporation). Epoxy compound having: Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, manufactured by Japan Epoxy Resin Co., Ltd. (currently, Mitsubishi Chemical Corporation, jER (registered trademark)) Series)), etc .; Bisphenol F type epoxy compounds such as Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.); Epicoat 152, Epicoat 1 4 (above, Japan Epoxy Resin Co., Ltd. (currently, Mitsubishi Chemical Co., Ltd., jER (registered trademark) series), EPPN201, EPPN202 (above, Nippon Kayaku Co., Ltd.) and other phenol novolac epoxy compounds; ECON -102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy Resin Co., Ltd. (currently manufactured by Mitsubishi Chemical Corporation) jER (registered trademark) series)) cresol novolac type epoxy compounds; V8000-C7 (made by DIC Corporation) naphthalene type epoxy compounds; Denacol EX-252 (made by Nagase ChemteX Corporation), CY175, CY177, CY179, Ara Daito CY-182, Araldite CY-192, Araldite CY-184 (above, manufactured by BASF), Epicron 200, Epicron 400 (above, made by DIC Corporation), Epicoat 871, Epicoat 872 (above, made by Japan Epoxy Resins Co., Ltd.) (Currently, Mitsubishi Chemical Corporation, jER (registered trademark) series)), ED-5661, ED-5661 (above, made by Celanese Coating Co., Ltd.), etc .; Denacol EX-611, Denacol EX -612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-312 (above, Nagase Chem Aliphatic polyglycidyl ether compounds such as Tex Corporation).
アミノ基の水素原子がメチロール基、アルコキシメチル基又はその両方で置換された基を有する、メラミン誘導体、ベンゾグアナミン誘導体又はグリコールウリルとしては、トリアジン環1個当たりメトキシメチル基が平均3.7個置換されているMX−750、トリアジン環1個当たりメトキシメチル基が平均5.8個置換されているMW−30(以上、株式会社三和ケミカル製);サイメル300、サイメル301、サイメル303、サイメル350、サイメル370、サイメル771、サイメル325、サイメル327、サイメル703、サイメル712等のメトキシメチル化メラミン;サイメル235、サイメル236、サイメル238、サイメル212、サイメル253、サイメル254等のメトキシメチル化ブトキシメチル化メラミン;サイメル506、サイメル508等のブトキシメチル化メラミン;サイメル1141のようなカルボキシ基含有メトキシメチル化イソブトキシメチル化メラミン;サイメル1123のようなメトキシメチル化エトキシメチル化ベンゾグアナミン;サイメル1123−10のようなメトキシメチル化ブトキシメチル化ベンゾグアナミン;サイメル1128のようなブトキシメチル化ベンゾグアナミン;サイメル1125−80のようなカルボキシ基含有メトキシメチル化エトキシメチル化ベンゾグアナミン;サイメル1170のようなブトキシメチル化グリコールウリル;サイメル1172のようなメチロール化グリコールウリル(以上、三井サイアナミッド株式会社製(現:日本サイテックインダストリーズ株式会社)等が挙げられる。 As the melamine derivative, benzoguanamine derivative, or glycoluril having a group in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both, an average of 3.7 methoxymethyl groups are substituted per triazine ring. MX-750 having an average of 5.8 substituted methoxymethyl groups per triazine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350, Methoxymethylated melamines such as Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712 and the like; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254 and other methoxymethylated butoxymethylated methy Minol; Butoxymethylated melamine such as Cymel 506, Cymel 508, etc .; Carboxy group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141; Methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123; Methoxymethylated butoxymethylated benzoguanamine; butoxymethylated benzoguanamine such as Cymel 1128; carboxymethyl-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80; butoxymethylated glycoluril such as Cymel 1170; Cymel 1172 Such as methylolated glycoluril (Mitsui Cyanamid Co., Ltd. (currently Japan Cytec Industries Co., Ltd.)) .
以上説明した本発明の剥離層形成用組成物を基体に塗布して加熱することで、高い耐熱性と、適度な柔軟性と、適度な線膨張係数とを有するポリイミドからなる薄膜(剥離層)を得ることができる。 A thin film (peeling layer) made of polyimide having high heat resistance, appropriate flexibility, and appropriate linear expansion coefficient by applying the composition for forming a release layer of the present invention described above to a substrate and heating it. Can be obtained.
ベース基体(基材)としては、例えば、ガラス、プラスチック(ポリカーボネート、ポリメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ、メラミン、トリアセチルセルロース、ABS、AS、ノルボルネン系樹脂等)、金属(シリコンウエハ等)、木材、紙、スレート等が挙げられる。 Examples of the base substrate (substrate) include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.) Wood, paper, slate and the like.
塗布する方法は、特に限定されるものではないが、例えば、キャストコート法、スピンコート法、ブレードコート法、ディップコート法、ロールコート法、バーコート法、ダイコート法、インクジェット法、印刷法(凸版、凹版、平版、スクリーン印刷等)等が挙げられる。 The coating method is not particularly limited, but for example, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate) , Intaglio, lithographic, screen printing, etc.).
また本発明の剥離層形成用組成物中に含むポリアミック酸をイミド化させる方法としては、基板上に塗布した組成物をそのまま加熱する熱イミド化、及び、組成物中に触媒を添加し加熱する触媒イミド化が挙げられる。 Moreover, as a method of imidizing the polyamic acid contained in the composition for forming a release layer of the present invention, thermal imidization in which the composition coated on the substrate is heated as it is, and a catalyst is added to the composition and heated. Examples include catalytic imidization.
ポリアミック酸の触媒イミド化は、本発明の剥離層形成用組成物中に触媒を添加し、攪拌することにより触媒添加組成物を調整した後、基板へ塗布、加熱することで樹脂薄膜(剥離層)が得られる。触媒の量はアミド酸基の0.1から30モル倍、好ましくは1から20モル倍である。また触媒添加組成物中に脱水剤として無水酢酸 等を加えることもでき、その量はアミド酸基の1から50モル倍、好ましくは3から30モル倍である。 The catalyst imidation of polyamic acid is performed by adding a catalyst to the release layer forming composition of the present invention and adjusting the catalyst addition composition by stirring, and then applying and heating the resin thin film (release layer). ) Is obtained. The amount of the catalyst is 0.1 to 30 mol times, preferably 1 to 20 mol times of the amic acid group. Further, acetic anhydride or the like can be added as a dehydrating agent to the catalyst additive composition, and the amount thereof is 1 to 50 mol times, preferably 3 to 30 mol times of the amic acid group.
イミド化触媒としては三級アミンを用いることが好ましい。三級アミンとしては、ピリジン、置換ピリジン類、イミダゾール、置換イミダゾール類、ピコリン、キノリン、イソキノリンなどが好ましい。 A tertiary amine is preferably used as the imidization catalyst. As the tertiary amine, pyridine, substituted pyridines, imidazole, substituted imidazoles, picoline, quinoline, isoquinoline and the like are preferable.
熱イミド化、及び触媒イミド化時の加熱温度は、450℃以下が好ましい。450℃を超えると、得られる樹脂薄膜が脆くなり、目的の用途に適した樹脂薄膜を得ることができない場合がある。
また、得られる樹脂薄膜の耐熱性と線膨張係数特性を考慮すると、塗布した組成物を50℃〜100℃で5分間〜2時間加熱した後に、そのまま段階的に加熱温度を上昇させて最終的に375℃超〜450℃で30分〜4時間加熱することが望ましい。
特に、塗布した組成物は、50℃〜100℃で5分間〜2時間加熱した後に、100℃超〜200℃で5分間〜2時間、次いで、200℃超〜375℃で5分間〜2時間、最後に375℃超〜450℃で30分〜4時間加熱することが好ましい。
加熱に用いる器具は、例えばホットプレート、オーブン等が挙げられる。加熱雰囲気は、空気下であっても不活性ガス下であってもよく、また、常圧下であっても減圧下であってもよい。
The heating temperature during thermal imidization and catalyst imidation is preferably 450 ° C. or lower. If it exceeds 450 ° C., the resulting resin thin film becomes brittle, and a resin thin film suitable for the intended use may not be obtained.
Moreover, considering the heat resistance and linear expansion coefficient characteristics of the resulting resin thin film, after heating the applied composition at 50 ° C. to 100 ° C. for 5 minutes to 2 hours, the heating temperature is increased stepwise as it is. It is desirable to heat at more than 375 ° C. to 450 ° C. for 30 minutes to 4 hours.
In particular, the applied composition is heated at 50 ° C. to 100 ° C. for 5 minutes to 2 hours, and then is over 100 ° C. to 200 ° C. for 5 minutes to 2 hours, and then is over 200 ° C. to 375 ° C. for 5 minutes to 2 hours. Finally, it is preferable to heat at over 375 ° C. to 450 ° C. for 30 minutes to 4 hours.
Examples of the appliance used for heating include a hot plate and an oven. The heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.
樹脂薄膜の厚さは、特に剥離層として用いる場合、通常0.01〜10μm程度、好ましくは0.05〜5μm程度であり、加熱前の塗膜の厚さを調整して所望の厚さの樹脂薄膜を形成する。 When used as a release layer, the thickness of the resin thin film is usually about 0.01 to 10 μm, preferably about 0.05 to 5 μm. The thickness of the coating film before heating is adjusted to a desired thickness. A resin thin film is formed.
以上説明した薄膜は、フレキシブル電子デバイスに適用される基板に損傷を与えることなく剥離させるための剥離層として使用するのに最適である。 The thin film described above is optimal for use as a peeling layer for peeling without damaging a substrate applied to a flexible electronic device.
本願の組成物により、フレキシブル電子デバイスに適用されるフレキシブル基板と、ベース基板との間に設けられる剥離層を形成することができる。ベース基板としては、ガラス又はシリコーンウェハを含むものが好ましく、より好ましくはガラスを含む。 With the composition of the present application, a release layer provided between a flexible substrate applied to a flexible electronic device and a base substrate can be formed. As a base substrate, what contains glass or a silicone wafer is preferable, More preferably, glass is included.
例えば、ガラス基板に本願の組成物を従来公知の手法により塗布し、得られた塗布膜を所定の温度で加熱することにより剥離層を形成することができる。
また、被剥離体層は、剥離層上に形成することができる。被剥離体層は、一層であっても複数層であってもよい。種々のデバイスを作製するには、複数層であるのが現実的である。
被剥離体層のうち剥離層直上の層は、用いる剥離層に依存するが、該剥離層との剥離性を良いもの、換言すると用いる剥離層との密着性が良くないもの、を用いるのがよい。
For example, the release layer can be formed by applying the composition of the present invention to a glass substrate by a conventionally known technique and heating the obtained coating film at a predetermined temperature.
Moreover, a to-be-separated body layer can be formed on a peeling layer. The layer to be peeled may be a single layer or a plurality of layers. In order to fabricate various devices, it is realistic to have a plurality of layers.
Of the layer to be peeled, the layer immediately above the release layer depends on the release layer to be used, but it is preferable to use a layer having good peelability with the release layer, in other words, a layer having poor adhesion to the release layer to be used. Good.
本願の他の面として、被剥離体の製造方法を提供する。
該方法は、
a)本願の組成物をガラス基板上に塗布した後、剥離層を形成する工程;
b)該剥離層上に、被剥離体を形成する工程;及び
c)剥離層と被剥離体との界面において、被剥離体を剥離する工程;
を有することにより、被剥離体を得ることができる。
b)工程において、「被剥離体」は一層であっても複数層であってもよい。なお、「被剥離体」のうち剥離層直上の層は、用いる剥離層に依存するが、該剥離層との剥離性を良いもの、換言すると用いる剥離層との密着性が良くないもの、であるのがよい。
As another aspect of the present application, a method for manufacturing an object to be peeled is provided.
The method
a) a step of forming a release layer after applying the composition of the present application on a glass substrate;
b) a step of forming an object to be peeled on the release layer; and c) a step of peeling the object to be peeled at the interface between the release layer and the object to be peeled;
It is possible to obtain an object to be peeled.
In the step b), the “object to be peeled” may be a single layer or a plurality of layers. In addition, although the layer immediately above the release layer of the “object to be peeled” depends on the release layer to be used, the release layer has good peelability, in other words, the adhesiveness to the release layer to be used is not good. There should be.
本発明の別の好ましい態様によれば、フレキシブル電子デバイスに適用される基板構造であって、
ベース基板と、
1又は2以上の領域で、前記ベース基体を覆う剥離層であって、本発明による剥離層形成用組成物により形成された剥離層と、
前記ベース基板と、前記剥離層を覆う、フレキシブル基板
とを含み、
前記フレキシブル基板と前記剥離層との密着力が、前記剥離層と前記ベース基体との密着力より大きいことを特徴とする、基板構造が提供される。ここでいう密着力の大きさは、例えば、本願の実施例で示したクロスカット試験により確認することができる。
According to another preferred aspect of the present invention, there is provided a substrate structure applied to a flexible electronic device,
A base substrate;
A release layer covering the base substrate in one or more regions, the release layer formed by the release layer forming composition according to the present invention;
Including the base substrate and a flexible substrate covering the release layer;
A substrate structure is provided in which the adhesive force between the flexible substrate and the release layer is greater than the adhesive force between the release layer and the base substrate. The magnitude | size of an adhesive force here can be confirmed by the crosscut test shown in the Example of this application, for example.
以下、本発明を実施例に沿って説明するが、本発明は該実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated along an Example, this invention is not limited to this Example.
本実施例に用いる略語について、以下に列挙し、説明する。
<溶媒>
NMP:N−メチルピロリドン。
<アミン類>
p−PDA:p-フェニレンジアミン。
APAB:2−(3−アミノフェニル)−5−アミノベンズイミダゾール。
DATP:4,4’−ジアミノ−p−ターフェニル。
6FAP:2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン。
Abbreviations used in this example are listed and described below.
<Solvent>
NMP: N-methylpyrrolidone.
<Amines>
p-PDA: p-phenylenediamine.
APAB: 2- (3-aminophenyl) -5-aminobenzimidazole.
DATP: 4,4′-diamino-p-terphenyl.
6FAP: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
<酸二無水物>
BPDA:3,3’−4,4’−ビフェニルテトラカルボン酸二無水物。
BA−TME:4,4-ビフェニレンビス(トリメリット酸モノエステル酸無水物)。
PMDA:ピロメリット酸二無水物。
<アルデヒド>
IPHA:イソフタルアルデヒド。
<Acid dianhydride>
BPDA: 3,3′-4,4′-biphenyltetracarboxylic dianhydride.
BA-TME: 4,4-biphenylenebis (trimellitic acid monoester anhydride).
PMDA: pyromellitic dianhydride.
<Aldehyde>
IPHA: isophthalaldehyde.
[数平均分子量及び重量平均分子量の測定]
ポリマーの重量平均分子量(以下「Mw」と略す)と分子量分布は、日本分光株式会社製GPC装置(Shodex(登録商標)カラムKF803LおよびKF805L)を用い溶出溶媒としてジメチルホルムアミドを流量1ml/分、カラム温度50℃の条件で測定した。なお、Mwはポリスチレン換算値とした。
[Measurement of number average molecular weight and weight average molecular weight]
The weight average molecular weight (hereinafter abbreviated as “Mw”) and molecular weight distribution of the polymer were determined by using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF805L) manufactured by JASCO Corporation and using dimethylformamide as an elution solvent at a flow rate of 1 ml / min. The measurement was performed at a temperature of 50 ° C. In addition, Mw was made into the polystyrene conversion value.
<合成例>
<合成例1 ポリイミド前駆体P1の合成>
BPDA(98)//p−PDA(90)/DATP(10)
p−PDA 17.8g(0.164モル)、DATP 2.38g(0.009モル)、およびAPAB 2.05g(0.009モル)をNMP 425gに溶解させ、BPDA 52.8g(0.179モル)を同時に添加した後、再度NMP 7.4gを添加し、窒素雰囲気下中23℃、24時間反応させた。得られたポリイミド前駆体P1のMwは63000、分子量分布9.9であった。
<Synthesis example>
<Synthesis Example 1 Synthesis of Polyimide Precursor P1>
BPDA (98) // p-PDA (90) / DATP (10)
17.8 g (0.164 mol) of p-PDA, 2.38 g (0.009 mol) of DATP, and 2.05 g (0.009 mol) of APAB were dissolved in 425 g of NMP, and 52.8 g (0.179) of BPDA. Mol) was added at the same time, and 7.4 g of NMP was added again, and the mixture was reacted at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polyimide precursor P1 was 63000 and molecular weight distribution 9.9.
<合成例2 ポリイミド前駆体P2の合成>
BPDA(98)/ DATP(100)
DATP 30.8g(0.118モル)をNMP 425gに溶解させ、BPDA 34.1g(0.116モル)を同時に添加した後、再度NMP 10gを添加し、窒素雰囲気下中23℃、24時間反応させた。得られたポリイミド前駆体P2のMwは70700、分子量分布9.7であった。
<Synthesis Example 2 Synthesis of Polyimide Precursor P2>
BPDA (98) / DATP (100)
30.8 g (0.118 mol) of DATP was dissolved in 425 g of NMP, 34.1 g (0.116 mol) of BPDA was added at the same time, 10 g of NMP was added again, and the reaction was performed in a nitrogen atmosphere at 23 ° C. for 24 hours. I let you. Mw of obtained polyimide precursor P2 was 70700 and molecular weight distribution 9.7.
<合成例3 ポリイミド前駆体P3の合成>
PMDA(98)/p−PDA(80)/DATP(20)
p−PDA 20.261g(0.1875モル)とTPDA 12.206g(0.0469モル)をNMP 617.4gに溶解し、15℃に冷却後、PMDA 50.112g(0.2298モル)を添加し、窒素雰囲気下、50℃で48時間反応させた。得られたポリイミド前駆体P3のMwは82,100、分子量分布は2.7であった。
<Synthesis Example 3 Synthesis of Polyimide Precursor P3>
PMDA (98) / p-PDA (80) / DATP (20)
p-PDA 20.261 g (0.1875 mol) and TPDA 12.206 g (0.0469 mol) were dissolved in 617.4 g of NMP, cooled to 15 ° C., and PMDA 50.112 g (0.2298 mol) was added. And reacted at 50 ° C. for 48 hours in a nitrogen atmosphere. Mw of the obtained polyimide precursor P3 was 82,100, and molecular weight distribution was 2.7.
<合成例4 ポリイミド前駆体P4の合成>
BP−TME(98)//p−PDA(95)/APAB(5)
p−PDA 9.66g(0.089モル)とAPAB 1.05g(0.005モル)をNMP 440gに溶解し、BP−TME 49.2g(0.092モル)を添加し、窒素雰囲気下、室温で24時間反応させた。得られたポリイミド前駆体P4のMwは57000、分子量分布は9.3であった。
<Synthesis Example 4 Synthesis of Polyimide Precursor P4>
BP-TME (98) // p-PDA (95) / APAB (5)
9.66 g (0.089 mol) of p-PDA and 1.05 g (0.005 mol) of APAB were dissolved in 440 g of NMP, 49.2 g (0.092 mol) of BP-TME was added, and under a nitrogen atmosphere, The reaction was allowed to proceed for 24 hours at room temperature. Mw of obtained polyimide precursor P4 was 57000, and molecular weight distribution was 9.3.
<合成例5 ポリイミド前駆体P5の合成>
BPDA(98)//p−PDA(100)
p−PDA 3.176g(0.02937モル)をNMP 88.2gに溶解し、BPDA 8.624g(0.02931モル)を添加した後、窒素雰囲気下、23℃で24時間反応させた。得られたポリイミド前駆体P5のMwは107,300、分子量分布4.6であった。
<Synthesis Example 5 Synthesis of Polyimide Precursor P5>
BPDA (98) // p-PDA (100)
3.176 g (0.02937 mol) of p-PDA was dissolved in 88.2 g of NMP, and 8.624 g (0.02931 mol) of BPDA was added, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polyimide precursor P5 was 107,300 and molecular weight distribution 4.6.
<合成例6 ポリベンゾオキサゾール前駆体(P6)の合成>
IHPA(98)//6FAP(100)
6FAP 3.18g(0.059モル)をNMP 70gに溶解し、IPHA 7.92g(0.060モル)を添加した後、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは107,300、分子量分布4.6であった。
<Synthesis Example 6 Synthesis of Polybenzoxazole Precursor (P6)>
IHPA (98) / 6/6 FAP (100)
6.18 g (0.059 mol) of 6FAP was dissolved in 70 g of NMP, and 7.92 g (0.060 mol) of IPHA was added thereto, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.
<合成例7 ポリイミド前駆体P7の合成>
PMDA(98)//p−PDA(100)
p−PDA 10.078g(93mmol)をNMP 220.0gに溶解させた。得られた溶液に、PMDA 19.922g(91mmol)を加え、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは55,900、分子量分布3.1であった。
<Synthesis Example 7 Synthesis of Polyimide Precursor P7>
PMDA (98) // p-PDA (100)
10.078 g (93 mmol) of p-PDA was dissolved in 220.0 g of NMP. PMDA 19.922g (91mmol) was added to the obtained solution, and it was made to react at 23 degreeC under nitrogen atmosphere for 24 hours. The obtained polymer had Mw of 55,900 and a molecular weight distribution of 3.1.
<剥離層基板の作製>
上記合成例1〜7で得たP1〜P7をNMPにて4wt%に希釈し、100mm×100mmガラス基板(OA−10G無アルカリガラス)又はシリコンウエハ上にスピンコーターを用いて塗布した後、キュア条件A〜Cで、オーブンで焼成し剥離層を作製した。
キュア条件A: 120℃で30分維持→昇温→300℃で60分維持→昇温→400℃で60分維持。なお、昇温速度は10℃/分であった。
キュア条件B: 120℃で30分維持→昇温→180℃で20分維持→昇温→240℃で20分維持→昇温→300℃で20分維持→昇温→400℃で20分維持→昇温→450℃で60分維持。なお、昇温速度は10℃/分であった。
キュア条件C: 80℃で10分維持→昇温→300℃で30分維持→昇温→400℃で30分維持。なお、昇温速度は10℃/分であった。
<Preparation of release layer substrate>
P1 to P7 obtained in Synthesis Examples 1 to 7 were diluted to 4 wt% with NMP, applied onto a 100 mm × 100 mm glass substrate (OA-10G non-alkali glass) or silicon wafer using a spin coater, and then cured. Under conditions A to C, baking was performed in an oven to prepare a release layer.
Cure condition A : maintained at 120 ° C. for 30 minutes → temperature increase → 300 ° C. for 60 minutes → temperature increase → 400 ° C. for 60 minutes. The temperature rising rate was 10 ° C./min.
Cure condition B : Maintain at 120 ° C. for 30 minutes → Temperature increase → Maintenance at 180 ° C. for 20 minutes → Temperature increase → Maintenance at 240 ° C. for 20 minutes → Temperature increase → Maintenance at 300 ° C. for 20 minutes → Temperature increase → Maintenance at 400 ° C. for 20 minutes → Temperature rise → Maintained at 450 ° C. for 60 minutes. The temperature rising rate was 10 ° C./min.
Cure condition C : maintained at 80 ° C. for 10 minutes → temperature rise → 300 ° C. for 30 minutes → temperature rise → 400 ° C. for 30 minutes. The temperature rising rate was 10 ° C./min.
得られた塗布膜の膜厚は、接触式膜厚測定器(株式会社ULVAC製Dektak 3ST)を使用し、測定した。
表1に、使用したP1〜P7の前駆体、塗布基板、キュア条件、および作製した剥離層の膜厚を示す。
The film thickness of the obtained coating film was measured using a contact-type film thickness measuring device (Dektak 3ST manufactured by ULVAC, Inc.).
Table 1 shows the P1-P7 precursors used, the coated substrate, the curing conditions, and the film thickness of the produced release layer.
<クロスカット試験I>
表1で示す実施例1〜5及び比較例1〜3の、剥離層を備えた基板について、クロスカット試験Iで、基板(ガラス又はシリコンウエハ)/剥離層の密着力を確認した。
クロスカット試験Iは、次のように行った。
(1)フィルム上に、1mm角の正方形を100個作製した。
(2)その後、粘着テープ(セロテープ(登録商標))で上記の正方形をはりつけ、剥離工程を行った。
(3)剥離工程後、基板に残存する、上記の正方形を数えた。
<Cross cut test I>
About the board | substrate provided with the peeling layer of Examples 1-5 and Comparative Examples 1-3 shown in Table 1, the adhesive force of the board | substrate (glass or silicon wafer) / peeling layer was confirmed by the crosscut test I.
The crosscut test I was performed as follows.
(1) On the film, 100 1 mm squares were produced.
(2) Thereafter, the above square was attached with an adhesive tape (cello tape (registered trademark)), and a peeling process was performed.
(3) After the peeling step, the squares remaining on the substrate were counted.
<クロスカット試験Iの結果の指標>
クロスカット試験の結果、剥離の程度を以下の指標で示す。
5B:剥離せず。
4B:5%以下の剥離。
3B:5〜15%の剥離。
2B:15〜35%の剥離。
1B:35〜65%の剥離。
0B:65%〜80%の剥離。
B:80%〜95%の剥離。
A:95%〜100%未満の剥離。
AA:100%の剥離。
<Index of results of crosscut test I>
As a result of the cross-cut test, the degree of peeling is indicated by the following index.
5B: Not peeled off.
4B: Peeling of 5% or less.
3B: 5-15% peeling.
2B: 15-35% peel.
1B: 35-65% peeling.
0B: 65% to 80% peeling.
B: 80% to 95% peeling.
A: 95% to less than 100% peeling.
AA: 100% peeling.
上記クロスカット試験Iとは別に、表1で示す実施例1〜5及び比較例1〜3の、剥離層を備えた基板について、該剥離層を構成する成分の特性、即ち(1)加熱時の重量変化における1%重量減少を示す温度、(2)波長1000nmでの屈折率、(3)波長1000nmでの複屈折、及び(4)表面エネルギー、を測定した。なお、各特性の測定条件などを以下に示す。 Apart from the cross-cut test I, the characteristics of the components constituting the release layer for the substrates having the release layer of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, that is, (1) When heated A temperature showing 1% weight loss in weight change of (2), (2) refractive index at a wavelength of 1000 nm, (3) birefringence at a wavelength of 1000 nm, and (4) surface energy were measured. The measurement conditions for each characteristic are shown below.
<(1)加熱時の重量変化における1%重量減少を示す温度>
ブルカー株式会社製 TD−DTA2000STを用いて、窒素雰囲気下で熱重量(TG)測定を行い、重量が1%減少する温度を求めた。
<(1) Temperature showing a 1% weight reduction in weight change during heating>
Using TD-DTA2000ST manufactured by Bruker Co., Ltd., thermogravimetric (TG) measurement was performed under a nitrogen atmosphere, and the temperature at which the weight decreased by 1% was determined.
<(2)波長1000nmでの屈折率及び(3)複屈折率>
高速分光エリプソメーターM−2000(ジェー・エー・ウーラム・ジャパン株式会社製)を用いて、屈折率及び復屈折率を測定した。なお、屈折率は、1000nmの値の面内屈折率とし、複屈折率は、面内屈折率と面外屈折率の差とした。
<(2) Refractive index at a wavelength of 1000 nm and (3) Birefringence>
The refractive index and the birefringence were measured using a high-speed spectroscopic ellipsometer M-2000 (manufactured by JA Woollam Japan Co., Ltd.). The refractive index was an in-plane refractive index having a value of 1000 nm, and the birefringence was a difference between the in-plane refractive index and the out-of-plane refractive index.
<(4)表面エネルギー>
全自動接触角計 DM−701(共和界面科学株式会社製)を用いて、各部材の表面エネルギーを測定した。なお、測定に用いた溶媒は、水とヨウ化メチレンであり、これらの溶媒の接触角から算出した。
<(4) Surface energy>
The surface energy of each member was measured using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). In addition, the solvent used for the measurement was water and methylene iodide, and was calculated from the contact angle of these solvents.
<被剥離体の形成とその剥離試験(クロスカット試験II)>
実施例1〜5及び比較例1〜3の、剥離層を備えた基板上に被剥離体を形成し、その剥離の程度をクロスカット試験IIで確認した。
<Formation of object to be peeled and peel test (cross-cut test II)>
The to-be-separated body was formed on the board | substrate provided with the peeling layer of Examples 1-5 and Comparative Examples 1-3, and the grade of the peeling was confirmed by the crosscut test II.
<<被剥離体層の作製>>
剥離層を備えた基板の該剥離層上に、被剥離体としてポリイミド層を形成した。
具体的には、表1に示す、実施例1〜5及び比較例1〜3の、剥離層を備える基板の、剥離層上に、上記合成例5又は合成例1で得られた前駆体P5又はP1をバーコーターで塗布した。その後、オーブンにて120℃で30分維持→昇温→180℃で20分維持→昇温→240℃/20分維持→昇温→300℃で20分維持→昇温→400℃で20分維持→昇温→450℃で60分維持(いずれの昇温においてもその速度は10℃/分であった)でキュアを行い、ポリイミドからなる膜厚15μmの被剥離体層を作製した。
<< Preparation of layer to be peeled >>
A polyimide layer was formed as an object to be peeled on the release layer of the substrate provided with the release layer.
Specifically, the precursor P5 obtained in Synthesis Example 5 or Synthesis Example 1 on the release layer of the substrate provided with the release layer of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1. Alternatively, P1 was applied with a bar coater. Then, maintain in an oven at 120 ° C. for 30 minutes → temperature increase → 180 ° C. for 20 minutes → temperature increase → 240 ° C./20 minute maintenance → temperature increase → 300 ° C. for 20 minutes → temperature increase → 400 ° C. for 20 minutes Maintenance → Temperature rise → Cure at 450 ° C. for 60 minutes (the speed was 10 ° C./min at any temperature rise) to produce a 15 μm-thick peeled layer made of polyimide.
<<クロスカット試験II>>
上記で得られた、被剥離体層及び剥離層を備える基板について、被剥離体層/剥離層間の密着力をクロスカット試験IIで確認した。
クロスカット試験IIは、クロスカット試験Iと同様に行った。
表2に、(1)加熱時の重量変化における1%重量減少を示す温度(表2中、「(1)」で表記する)、(2)波長1000nmでの屈折率(表2中、「(2)」で表記する)、(3)該(2)の屈折率と複屈折との差(表2中、「(3)」で表記する)、(4)表面エネルギー(表2中、「(4)」で表記する。ただし、単位はdyne/cmである)、被剥離体層で用いたポリイミド前駆体、並びにクロスカット試験I及びIIの結果を示す。
<< Crosscut Test II >>
About the board | substrate provided with the to-be-separated body layer and the peeling layer obtained above, the adhesive force between a to-be-separated body layer / peeling layer was confirmed by the crosscut test II.
The crosscut test II was performed in the same manner as the crosscut test I.
Table 2 shows (1) a temperature indicating a 1% weight decrease in weight change during heating (indicated by “(1)” in Table 2), (2) a refractive index at a wavelength of 1000 nm (in Table 2, “ (2) ”, (3) difference between the refractive index and birefringence of (2) (indicated by“ (3) ”in Table 2), (4) surface energy (in Table 2, This is indicated by “(4)” (where the unit is dyne / cm), the polyimide precursor used in the peeled layer, and the results of cross-cut tests I and II.
*: 比較例2の複屈折は測定できなかった。
**: 比較例1及び比較例3のクロスカット試験IIは、剥離層および基板との密着性が低いため、測定できなかった。
*: The birefringence of Comparative Example 2 could not be measured.
**: The crosscut test II of Comparative Example 1 and Comparative Example 3 could not be measured due to low adhesion to the release layer and the substrate.
表2から次のことがわかる。実施例1〜5の剥離層は、試験Iの結果が5Bであることから、基板から剥離層が剥がれることがない一方、試験IIの結果がAAであることから、剥離層から被剥離体層のみが剥離することがわかる。要するに、本発明の剥離層用組成物から形成された剥離層は、所望の剥離結果をもたらすことがわかる。
一方、比較例1及び比較例3は、試験Iの結果がAAであるため、剥離層が基板から剥離することがわかる。要するに、比較例1及び比較例3は、所望の剥離結果を得ることができないことがわかる。また、比較例2は、試験I及び試験IIが共に5Bであることから、剥離層と基板との界面においても、剥離層と被剥離体層との界面においても剥離せず、所望の剥離結果を得ることができないことがわかる。
Table 2 shows the following. In the peeling layers of Examples 1 to 5, since the result of Test I is 5B, the peeling layer is not peeled off from the substrate, while the result of Test II is AA. It turns out that only peels. In short, it can be seen that the release layer formed from the composition for release layer of the present invention provides a desired release result.
On the other hand, Comparative Example 1 and Comparative Example 3 show that the release layer peels from the substrate because the result of Test I is AA. In short, it can be seen that Comparative Example 1 and Comparative Example 3 cannot obtain a desired peeling result. In Comparative Example 2, since both Test I and Test II are 5B, neither the interface between the release layer and the substrate nor the interface between the release layer and the layer to be peeled is peeled off. It can be seen that cannot be obtained.
Claims (14)
[式中、X1は、4価の有機基を表し、Y1は、下記の式(P)で表される2価の基を表す:
(式中、Rは、F、Cl、炭素数1〜3のアルキル基、又はフェニル基を表し、mは、0〜4の整数を表し、かつ、rは1〜4の整数を表す)]。 The composition for peeling layer formation containing the polyamic acid which contains 50 mol% or more of monomer units represented by following formula (1), and whose weight average molecular weight is 10,000 or more, and an organic solvent.
[Wherein, X 1 represents a tetravalent organic group, and Y 1 represents a divalent group represented by the following formula (P):
(In the formula, R represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, m represents an integer of 0 to 4, and r represents an integer of 1 to 4)] .
(式中、
R1、R2、R3、R4、R5及びR6は、同一であっても異なっていてもよく、F、Cl、炭素数1〜3のアルキル基、又はフェニル基を表し、
m1、m2、m3、m4、m5及びm6は、同一であっても異なっていてもよく、0〜4の整数を表す)。 The composition for peeling layer formation of Claim 1 whose said Y1 is a bivalent group represented by either of following formula (P1)-(P3).
(Where
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group,
m1, m2, m3, m4, m5 and m6 may be the same or different and represent an integer of 0 to 4).
[式中、
X1は、請求項1で定義されたとおりであり、Y2は、下記の式(P4)で表される基を表す:
(式中、
R7、及びR8は、同一であっても異なっていてもよく、F、Cl、炭素数1〜3のアルキル基、又はフェニル基を表し、
R’は、水素原子、炭素数1〜3のアルキル基、又はフェニル基を表し、
lは、0〜4の整数を表し、かつ
mは、請求項1で定義されたとおりである)]。 The composition for peeling layer formation as described in any one of Claims 1-3 in which the said polyamic acid further contains the monomer unit represented by following formula (2).
[Where:
X 1 is as defined in claim 1 and Y 2 represents a group represented by the following formula (P4):
(Where
R 7 and R 8 may be the same or different and each represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group;
R ′ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group,
l represents an integer from 0 to 4 and m is as defined in claim 1)].
(式中、Ra及びRbは同一であっても異なっていてもよく、炭素数1〜4のアルキル基を表し、hは自然数を表す)。 The composition according to any one of claims 1 to 6, wherein the organic solvent is a solvent represented by the following formula (A) or (B).
(In the formula, R a and R b may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and h represents a natural number).
請求項1〜9のいずれか一項に記載の剥離層形成用組成物を用いて作製される、剥離層。 A release layer formed between a flexible substrate applied to a flexible electronic device and a base substrate,
A release layer produced using the release layer forming composition according to claim 1.
ベース基板と、
1又は2以上の領域で、前記ベース基体を覆う剥離層であって、請求項1〜9のいずれか一項に記載の剥離層形成用組成物により形成された剥離層と、
前記ベース基板と、前記剥離層を覆う、フレキシブル基板
とを含み、
前記フレキシブル基板と前記剥離層との密着力が、前記剥離層と前記ベース基体との密着力より大きいことを特徴とする、基板構造。 A substrate structure applied to a flexible electronic device,
A base substrate;
A release layer covering the base substrate in one or more regions, the release layer formed by the release layer forming composition according to any one of claims 1 to 9,
Including the base substrate and a flexible substrate covering the release layer;
A substrate structure, wherein an adhesion force between the flexible substrate and the release layer is larger than an adhesion force between the release layer and the base substrate.
ベース基板を準備する工程、
1又は2以上の領域で、前記ベース基体を覆う剥離層を、請求項1〜9のいずれか一項に記載の剥離層形成用組成物を用いて作製する工程、
前記ベース基板と、前記剥離層上に、フレキシブル基板を形成する工程
を含み、
前記フレキシブル基板と前記剥離層との密着力が、前記剥離層と前記ベース基体との密着力より大きいことを特徴とする、作製方法。
A method for producing a substrate structure applied to a flexible electronic device,
Preparing a base substrate,
The process of producing the peeling layer which covers the said base base | substrate in the area | region of 1 or 2 or more using the composition for peeling layer formation as described in any one of Claims 1-9,
Forming a flexible substrate on the base substrate and the release layer;
The manufacturing method characterized by the adhesive force of the said flexible substrate and the said peeling layer being larger than the adhesive force of the said peeling layer and the said base base | substrate.
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WO2015152120A1 (en) | 2015-10-08 |
KR20160142331A (en) | 2016-12-12 |
CN108690495A (en) | 2018-10-23 |
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CN106133077B (en) | 2018-11-06 |
CN106133077A (en) | 2016-11-16 |
CN108690494A (en) | 2018-10-23 |
CN108690495B (en) | 2021-05-25 |
KR20210154273A (en) | 2021-12-20 |
JPWO2015152120A1 (en) | 2017-04-13 |
TW201927925A (en) | 2019-07-16 |
KR102467104B1 (en) | 2022-11-14 |
KR102340689B1 (en) | 2021-12-16 |
KR102467105B1 (en) | 2022-11-14 |
JP2019143143A (en) | 2019-08-29 |
CN108690494B (en) | 2021-04-06 |
JP6775769B2 (en) | 2020-10-28 |
TW201610036A (en) | 2016-03-16 |
TWI669356B (en) | 2019-08-21 |
KR20210156292A (en) | 2021-12-24 |
TW201927861A (en) | 2019-07-16 |
JP6775768B2 (en) | 2020-10-28 |
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TWI690545B (en) | 2020-04-11 |
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